Anreicherung von Metallionen durch Membranfiltration von Polyelektrolytkomplexen

The separation of heavy metals by complexation with macromolecular water-soluble agents and subsequent ultrafiltration is described. The method can be expected to join common techniques of metal separation like liquid-liquid extraction, adsorption, redox reaction or liquid membrane permeation. Reactions between metal ions and polymer phases are characterized as pH-dependent distribution equilibria illustrated at a propene-maleic acid copolymer as an example. The complexation behaviour of the substance under study is governed by isotherms of the saturation type. Attempts proved to be successful to calculate break-through constants as well as saturation capacities from batch-type studies and dynamic measurements by transferring the laws of adsorption and ion exchange, respectively, to the ultrafiltration process. The quantities of fixed metals amounting to about 2.5 mmol/g were found to be in the range of moderate adsorbents. A solution consisting of 3 solutes has been tested to get more detailed information on mixture behaviour as compared to single component systems. In the long run, the proposed method should provide an additional variant for the extraction and concentration of metal ions from diluted aqueous solutions.     

Auswirkung von Schwermetallgemischen auf die biologische Behandlung naphthalinsulfonsäurehaltiger Abwässer

Effect of Mixtures of Heavy Metals on the Biological Treatment of Sewages Containing Naphthalenesulfonic Acid Biological wastewater treatment processes can be destabilized considerably by heavy metals. In this investigation, the effect of loadings of heavy metals on the degradation of naphthalene-2-sulfonic acid (2NS) by immobilized bacteria in continuously operated airlift-loop reactors was studied. Shock loadings with mixtures of cadmium and nickel, or cadmium and zinc, respectively, resulted in increases in inhibition compared to those observed with the single metals. In contrast, the 2NS-degradation was less inhibited by shock loadings with mixtures of nickel and zinc than by the single metal ions. Repeated shock loadings up to 100 mg L^?1 nickel and 1000 mg L^?1 zinc effected an adaptation of the microorganisms. Continuous loadings with up to 10 mg L^?1 cadmium and nickel each, or with 50 mg L^?1 nickel and 210 mg L^?1 zinc, respectively, did not inhibit the degradation of 2NS. The permanent loadings led to an adaptation of the bacteria with an increased biosynthesis of proteins from 0.2 to 0.5 g g^?1 cell dry weight. However, if the immobilized cells were incubated with mixtures of cadmium and nickel, the specific polysaccharide content decreased to less than 0.2 g g^?1 cell dry weight, resulting in a detachment of the biofilms.     

Eliminierung von Schwermetallen aus komplexbildnerhaltigen Abwässern durch Kalk-/Kreide-Fällung

A report is given on laboratory investigations into model waters containing Cu²⁺-, Ni²⁺- or Zn²⁺-ions and tartrate, citrate, NTA or EDTA as complexing agents. There were determined residual concentrations of the metal ions at different shares of complexing agents, which are achieved by the precipitation with lime and chalk. Chalk is added in order to secure the required exess of calcium ions without causing an overalkalinization of the water. In the range of pH = 8…9, however, residual concentrations lower than 1 mg/1 are achieved only for copper ions in the presence of tartrate.     

The Role of Particulate Matter in the Mobilization of Trace Metals during Anaerobic Digestion of Solid Waste Material Die Bedeutung der partikulären Substanz für die Mobilisierung von Spurenmetallen beim anaeroben Abbau fester Abfallstoffe

Metal ions bound to particulate matter represent the greatest portion (i.e. > 95%) of the total metal content found in leachate from reactor experiments where solid waste material was anaerobically digested. This seems true even though strong complexing agents are in solution which increase the solubility of Pb and Cu by a factor up to 10⁴… 10⁵ over that theoretically predicted according to the solubility of the corresponding sulfide mineral. A titrimetric characterization of the metal ion binding sites of the particulate matter suggests that the metal binding properties of the particulate matter are mainly due to organic, aminoacid-type compounds (amines. thio groups, carboxylic groups) probably of bacterial origin. The change of the concentration of the binding sites with time, together with the change of the composition of the particulate matter indicates that bacterial flocs are suspended in the leachate during the switch from acidogenic to methanogenic conditions — either due to the detachment of bacterial films from the solid material by the intensive gas production or due to the formation of syntrophic methanogenic bacterial associations or a combination of both. A combination of the two factors, strong affinity of bacterial mass to metal ions on the one hand, and suspending of the bacterial mass in the leachate on the other hand, will therefore imply a great mobilizing potential for trace metals. Consequently, the highest concentrations of particulate bound Cd were found in reactor experiments where sewage sludge contaminated with Cd was added to the waste material. An increase of the concentration of dissolved cadmium over the solubility of cadmium sulfide, however, could not be observed.     

Assessment of Metal Pollution in Water and Surface Sediments of the Seyhan River,Turkey, Using Different Indexes

The aim of this study was to assess the level of heavy metals (Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) contamination and enrichment in the surface sediments of the Seyhan River, which is the receiving water body of both treated and untreated municipal and industrial effluents as well as agricultural drainage waters generated within Adana, Turkey. Sediment and water samples were taken from six previously determined stations covering the downstream of the Seyhan dam during both wet and dry seasons and the samples were then analyzed for the heavy metals of concern. When both dry and wet seasons were considered, metal concentrations varied significantly within a broad range with Al, 7210–33 967 mg kg^?1 dw; Cr, 46–122 mg kg^?1 dw; Cu, 6–57 mg kg^?1 dw; Fe, 10 294–26 556 mg kg^?1 dw; Mn, 144–638 mg kg^?1 dw; Ni, 82–215 mg kg^?1 dw; Pb, 11–75 mg kg^?1 dw; Zn, 34–146 mg kg^?1 dw in the sediments while Cd was at non‐detectable levels for all stations. For both seasons combined, the enrichment factor (EF) and the geo‐accumulation index (I_geo) for the sediments in terms of the specified metals ranged from 0.56 to 10.36 and ?2.92 to 1.56, respectively, throughout the lower Seyhan River. The sediment quality guidelines (SQG) of US‐EPA suggested the sediments of the Seyhan River demonstrated “unpolluted to moderate pollution” of Cu, Pb, and Zn, “moderate to very strong pollution” of Cr and Ni. The water quality data, on the other hand, indicated very low levels of these metals suggesting that the metal content in the surface sediments were most probably originating from fine sediments transported along the river route instead of water/wastewater discharges with high metal content.     

Metal Ion Extraction with Bipyridine Derivatives as Chelating Ligands in Supercritical Carbon Dioxide

Three fluorinated bipyridine ligands have been designed and synthesized as chelating agents for the extraction of metal ions in supercritical CO₂ (sc‐CO₂). The ligand solubilities in sc‐CO₂ were investigated at different temperatures and pressures, and the measured data have been correlated using a semiempirical model. The calculated results showed satisfactory agreement with the experimental data. Based on these data, metal ion extraction with the three compounds as chelating agents in sc‐CO₂ was performed from spiked filter paper, whereby ligand 1 showed the highest extraction efficiency, especially for Ni²⁺ and Cu²⁺. The extraction constants, K_ex, of the three chelating ligands were seen to increase with increasing extraction efficiency for the same metal ion in the same extraction system.     

Untersuchung der Sorptionseigenschaften des Kationenaustauschers KB-2M mit Makronetzstruktur zur Abtrennung von Zinkionen aus Ab- und Spülwässern

Study of Sorptional Properties of the Cation Exchanger KB-2M with Macroreticular Structure for Recovery of Zinc Ions from Sewage and Rinsing Water Although a number of ion-exchange methods have been employed for the recovery of some transition metals from industrial effluents, knowledge about ion-exchange resins with macroreticular structure is poor. The present paper describes the mechanism of sorption on such exchangers and their application for recovery of zinc from sewage rinsing water. Ion exchanger of macroreticular structure are polymers with long-chained cross-linking agents. We have synthesized carboxylic ion-exchange resins by hydrolysis of copolymerisates of methyl acrylate with different cross-linking agents: divinylbenzene, divinyl sulfide, divinyl ester of ethylene glycol and divinyl ester of di- or triethylene glycol. The sorption process on modifications of the carboxylic resins KB-2 of various structure was studied with different methods: potentiometric titration, infrared spectroscopy, electron microscopy, X-ray structural analysis. The initial zinc concentration in rinsing water was 0.05 mol/L at pH from 3 to 6. For the sorption, 0.2…1.0 g of resin were equilibrated with 100 mL of zinc solution. After equilibrium (12 h), the resin was separated from solution. The zinc ions were determined by atomic absorption spectrometry after stripping with 100 mL of 10% sulfuric acid. The distribution ratio D was calculated (D: mmole of Zn sorbed per gram of resin divided by mmole of Zn per millilitre of solution). By means of infrared spectroscopy, the mechanism of sorption of zinc ions from rinsing water was determined. There may be a possibility of the formation of complexes in the cation-exchange resin phase. It was found out in this paper that the cation-exchanger KB-2M of macroreticular structure is the most effective for the sorption of the Zn²⁺-ions from sewage and rinsing water.     

A Novel Concept for the Removal of Solvent Vapors from Exhaust Air

The emission of large amounts of solvent vapors with exhaust air from industrial production into the environment is a serious problem. In Germany, industry‐sector‐specific threshold values are applied and technical measures for pollution reduction are required. Different techniques for exhaust air cleaning are in use but still posing problems concerning costs and reliability. For these reasons, the development of processes for exhaust air treatment is the subject of the current research. A new concept for exhaust air cleaning is introduced that combines absorption of a solvent vapor by an organic fluid and a subsequent adsorption by a molecular sieve placed in the absorber. It was managed to close the loops of solvent recovery and sorbents regeneration. In laboratory‐scale experiments it was possible to reduce an initial ethylacetate pollution of 800 mg/m³ or 349 mg C/m³ below the limit value of 75 mg C/m³ over 60 h duration. Thermogravimetric measurements assisted to define optimum conditions for solvent recovery at 180°C from the molecular sieve. One unexpected positive finding was the considerable increase in the solvent release in the presence of the absorption fluid while adsorption isotherms revealed first insight into this process.     

Hysteresis‐based analysis of overland metal transport

Introducing a concept of equivalent mass depth of flow, this study describes the phenomenon of non‐point source pollutant (metal) transport for pavement (or overland) flow in analogy with wave propagation in wide open channels. Hysteretic and normal mass rating curves are developed for runoff rate and mass of 12 dissolved and particulate‐bound metal elements (pollutants) using the rainfall‐runoff and water quality data of the 15 × 20 m² instrumented pavement in Cincinnati, USA. Normal mass rating curves developed for easy computation of pollutant load are found to be of a form similar to Manning's, which is valid for open channel flows. Based on the hysteresis analysis, wave types for dissolution and mixing of particulate‐bound metals are identified. The analysis finds that the second‐order partial‐differential equation normally used for metal transport does not have the efficacy to describe fully the strong non‐linear phenomena such as is described for various metal elements by dynamic waves. In addition, the proportionality concept of the popular SCS‐CN concept is extended for determining the potential maximum metal mass M_p of all the 12 elements transported by a rain storm and related to the antecedent dry period (ADP). For the primary metal zinc element, M_p is found to increase with the ADP and vice versa. Copyright © 2003 John Wiley & Sons, Ltd.     

Removal of Heavy Metals from Synthetic Mixture as well as Pharmaceutical Sample Via Cation Exchange Resin Modified with Rhodamine B: Its Thermodynamic and Kinetic Studies

A new sorbent was prepared by loading rhodamine B on Amberlite IR‐120. Various physico‐chemical parameters such as effects of adsorbate concentration, contact time, pH, and temperature on the sorption of the dye have been studied. Thermodynamic parameters (ΔH° and ΔS°) were also evaluated for the sorption of dye. Kinetic studies revealed that the sorption of the dye was best fit for pseudo‐second‐order kinetic. The metal ion uptake in different solvent systems has been explored through column studies. On the basis of distribution coefficient (K_d), some heavy metal ions of analytical interest from binary mixtures have been separated. The limit of detection (LOD) for the Ni²⁺ and Fe³⁺ metal ions was 0.81 and 0.60 µg L^?1, and the limit of quantification (LOQ) was found to be 2.72 and 2.0 µg L^?1. This sorbent has also been successfully applied in the analysis of multivitamin formulation. The applicability of the modified resin in the separation of heavy metals constituting real and synthetic samples has been explored.     

Comparative Toxicity of Heavy Metals and Interaction of Metals on a Freshwater Pulmonate Snail Lymnaea acuminata (Lamarck)

In static bioassays the toxicity of heavy metal ions against Lymnaea acuminata over 24 … 96 h is tested. The values of the LC_50,96h for the metals tested are, in mg/l: Hg²⁺ ?0.023; Cu²⁺-0.034, Cd²⁺ ?0.872, Ni²⁺ ?2.78, Cr⁶⁺ ?5.97 and Zn²⁺ ?10.49. In the combined solutions of Cu²⁺, Ni²⁺ and Zn²⁺ at least an additive effect of toxicity occurs in the presence of two metals. The same holds for the presence of the three metals; in this case, the relative toxicity against the mixture of two metallic salt solutions appears to be slightly reduced. The acute manifestation of the toxic effect occurs within 48 h, subsequently the relative mortality decreases especially in the mixed solutions.     

Festkontaktierte potentiometrische Elektroden für Sulfatbestimmungen in wässrigen Lösungen

Solid‐contacted Potentiometric Electrodes for Measurements of Sulfate Ions in Aqueous Solutions A solid‐contact electrode for potentiometric measurement of sulfate ions in aqueous solutions was developed and examined. The electrode is based on a PVC membrane which contains the ionophore 3‐decyl‐1,5,8‐triazacyclodecan‐2,4‐dione (DTADD). Instead of the usual inner fluid junction, a polypyrrole layer applied on the inner side of the PVC membrane was employed as inner solid contact. The performance of this electrode was compared to solid‐state sulfate‐selective electrodes with the ionophore α,α′‐bis(N′‐phenylthioureylene)‐m‐xylene (BTH) and to electrodes in the coated‐wire configuration. For the parameters sensitivity, selectivity, and long‐term stability, electrodes with the DTADD ionophore show improved properties. In the sulfate concentration range of 5·10^–5...10^–2 mol L^–1 the slope of the response is –(26.8 ± 0.5) mV/decade. The new solid contact sulfate electrodes showed a very low drift of the electrode potential within a period of 150 days when the electrode was stored in 10^–2 M Na₂SO₄. In Na2SO4 solutions of the pH range of 4...9 the electrode potentials were constant. The 95% response time was about 10 s when the sulfate concentration was changed from 10^–4 mol L^–1 to 10^–3 mol L^–1. The selectivity with DTADD ionophore relating to the nitrate ions is higher than the selectivity with BTH. Improvements are also made in comparison with sulfate‐selective electrodes described in the literature which contain other ionophores with fluid inner reference electrolytes.     

Sensitive Ion‐Flotation Separation of Ag(I) Traces Using 2‐(2‐Methoxyphenyl)benzimidazole before Flame Atomic Absorption Spectrometric Determination in Water

A sensitive, reliable, and environmentally friendly method for simple separation and preconcentration of Ag(I) traces in aqueous samples is presented prior to their flame atomic absorption spectrometric determinations. At pH 7.0, Ag(I) was separated with 2‐(2‐methoxyphenyl)benzimidazole (MPBI) as a new complexing agent and floated after adding sodium dodecyl sulfate (SDS) as a foaming reagent. The floated layer was then dissolved in proper amount of concentrated nitric acid in methanol and introduced to the flame atomic absorption spectrometer (FAAS). The effects of pH, concentration of MPBI, type and amount of surfactant as the floating agent, type and amount of eluting agent, and influence of foreign ions on the recovery of the analyte ion were investigated. Also, using a nonlinear curve fitting method, the formation constant of 1.62 × 10⁶ was obtained for Ag(I)–MPBI complex. The analytical curve was linear in the range of 1.8 × 10^?7–1.7 × 10^?6 mol/L for determination of Ag(I). The relative standard deviation (RSD; N = 10) corresponding to 0.7 × 10^?6 mol/L of Ag(I), the limit of detection (10 blanks), and the enrichment factor were obtained as 1.7%, 2.9 × 10^?8 mol/L, and 43.0, respectively. The proposed procedure was then applied successfully for determination of silver ions in different water samples.     

Historical fluxes of metal and metalloids in an aquatic ecosystem affected by land-use change and mining activities in northwestern Mexico

Freshwater reservoirs are essential owing because of their ecological, economic, and social importance. They are particularly vulnerable to contamination, as of metal and metalloids, derived from anthropogenic activities like mining. The temporal variations in trace element concentrations (arsenic (As), mercury (Hg), chromium (Cr), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn)), enrichment, fluxes, and possible sources were evaluated by studying two sediment cores from the La Angostura (ANG) Reservoir (northwest Mexico), using ²¹⁰Pb geochronology. The enrichment factors showed from null to minor enrichment for most elements, but moderate to severe enrichment of mercury (Hg). Most trace element concentrations had a detrital origin, and notable Hg concentration increases since the past decade were associated with severe drought periods, likely resulting from wildfires. The observed sediment concentrations of As and Hg can cause adverse effects on biota in the ecosystem since they are above the probable effect level (PEL). Development of strategies for metal attenuation in this reservoir is recommended and metals should be controlled until specific ecotoxicological studies are performed.     

Combined ESR and EISCAT observations of the dayside polar cap and auroral oval during the May 15, 1997 storm

The high-latitude ionospheric response to a major magnetic storm on May 15, 1997 is studied and different responses in the polar cap and the auroral oval are highlighted. Depletion of the F₂ region electron density occurred in both the polar cap and the auroral zone, but due to different physical processes. The increased recombination rate of O⁺ ions caused by a strong electric field played a crucial role in the auroral zone. The transport effect, however, especially the strong upward ion flow was also of great importance in the dayside polar cap. During the main phase and the beginning of the recovery phase soft particle precipitation in the polar cap showed a clear relation to the dynamic pressure of the solar wind, with a maximum cross-correlation coefficient of 0.63 at a time lag of 5 min.     

Spatial and Temporal Distribution of Dust‐Bound Trace Metal Elements around Kuhdasht Watershed Area in Iran

Dust, as a source of trace metal elements, affects the health of society. The spatial and temporal concentrations of dust‐bound trace metals (Cd, Pb, Ni, Zn, Cu, and Mn) in Kuhdasht watershed (456 km²), Lorestan Province, Iran, is investigated. Dust is collected using glass traps placed in ten research stations in the region. The spatial and temporal distribution of dust trace metals are plotted using ARC‐GIS. The highest and the lowest concentrations of Zn (9751150 mg kg^?1), Pb (46.352.9 mg kg^?1), and Cd (2.443.30 mg kg^?1) are obtained in winter, of Ni (98110 mg kg^?1) and Cu in autumn (16.053.5 mg kg^?1), and of Mn in summer (385505 mg kg^?1). The spatial concentrations of dust‐bound trace metals indicate all, except Cu, show a decreasing trend from the mountains toward the plains, similar to that of soil and of dust, except for Zn, which shows higher concentrations in dust than in soil. The potential sources of dust‐bound trace metals and their rate of contamination are also investigated using the enrichment and contamination factors. The major sources of Cd and Zn in the dust of watershed are due to anthropogenic activities or from activities outside the borders.     

Modelling catchment‐scale erosion patterns in the East African Highlands

Prompt location of areas exposed to high erosion is of the utmost importance for soil and water conservation planning. Erosion models can be useful tools to locate sources of sediment and areas of deposition within a catchment, but the reliability of model predictions of spatial patterns of erosion at catchment scale has seldom been validated against observations. This study aimed to evaluate the performance of a simple empirical model (Morgan, Morgan and Finney model, MMF) in predicting spatial patterns of erosion at two small catchments in the East African Highlands: Kwalei (Tanzania) and Gikuuri (Kenya). Erosion maps predicted by the MMF model were compared with erosion maps obtained by direct survey. In Kwalei, erosion features were especially frequent in fields of annual crops. In Gikuuri, slope was the critical erosion factor, with estimated erosion rates >10 kg m^?2 a^?1 on slopes >18 per cent. Predicted erosion rates were mainly transport‐limited and ranged from <0·01 to 13·50 kg m^?2 a^?1 in Kwalei and 9·29 kg m^?2 a^?1 in Gikuuri. The performance of the MMF model in predicting the spatial patterns of erosion was acceptable in Kwalei, but poor in Gikuuri. However, by excluding the elements at the valley bottoms in Gikuuri Catchment, the performance of the model improved dramatically. The spatial pattern of erosion predicted by the MMF model was driven by the accumulation of surface runoff, which did not consider the possibility of re‐infiltration along the slope. As a result, the MMF erosion patterns predicted by the model increased invariably from the ridges to the valley bottoms, hampering the model suitability for locating areas subjected to high and very high erosion. It is concluded that the model predictions could be substantially improved by introducing a more realistic hydrological component for the prediction of surface runoff along the hill‐slope. Copyright © 2005 John Wiley & Sons, Ltd.     

Simultaneous Organic Matter and Nitrogen Removal from Piggery Slaughterhouse Wastewater Using Bioaugmented Gaslift Membrane Bioreactor

A single bioaugmentation reactor and a side-stream gaslift membrane bioreactor combined with bioaugmentation are conducted to treat real wastewater from a centralized piggery slaughterhouse in Vietnam. The bioaugmented reactor is inoculated with heterotrophic microorganisms (Bacillus sp.) isolated from piggery slaughterhouse wastewater. The results of a single bioaugmentation experiment show high removal efficiency of chemical oxygen demand (COD) (84.8%–97.5%) and total nitrogen (TN) (69.9%–87.2%) at loading rates of 1.28–3.89 and 0.14–0.37 kg m⁻³ d⁻¹, respectively. The combined system demonstrates a significantly higher TN removal efficiency (89.0%–96.1%) (p < 0.001), more stable flux (36.0–38.4 L m⁻² h⁻¹), and transmembrane pressure (0.95–1.05 bar), and better capacity of separation of solid–liquid phases compared to the single bioaugmentation. High COD and TN removal efficiency is possibly due to assimilation and simultaneous nitrification and denitrification processes. The results of this study also indicate the feasibility and propitious efficiency of the bioaugmented gaslift membrane bioreactor for piggery slaughterhouse wastewater treatment.     

Episodic mantle differentiation: Nd and Sr isotopic evidence

Clinopyroxenes separated from two hydrous and four anhydrous ultramafic nodules, selected from a suit of xenoliths from Dreiser Weiher (DW), West Germany, have been studied for Nd and Sr isotopic composition. Nd exhibits a range of ε_JUV(T) from 0 to +12.4 and ⁸⁷Sr/⁸⁶Sr varies between 0.70185 and 0.70400. T_ICE model ages for anhydrous nodules indicate that the mantle underlying DW was originally depleted ?2 AE ago. Correlation of ¹⁴³Nd/¹⁴⁴Nd with Sm/Nd in this group of samples suggests that a second partial melting event occurred about 560 m.y. ago resulting in LREE enrichment of at least part of the anhydrous mantle. During a later episode, probably contemporaneous with the eruption of the host basalt in Quaternary times, most of the spinel peridotitic upper mantle below DW was modified. This metasomatism led to hydration and incompatible element enrichment of originally anhydrous mantle. The isotopic data for the anhydrous nodules again demonstrate that oceanic-type mantle underlies at least some continental areas. It is apparent that the separation of subcontinental mantle regions from an initially chondritic reservoir may occur in several discrete episodes. However, differing histories of depletion and/or enrichment will produce isotopically distinct mantle reservoirs. Therefore, basalts extracted from these mantle reservoirs will scatter about an average Nd-Sr trend line reflecting the nature of the differentiation in their source regions.