Vergleich ausgewählter Elutionsverfahren zur Beurteilung der Mobilität von Metallen

Comparison of Selected Elution Procedures for the Valuation of the Mobility of Metals from Sediment and Sewage Sludge Several methods of extraction are generally used to evaluate environmental or ecological toxicity and deposition of waste material. In this paper, the application of the German standard methods DIN 38414-S7, DIN 38414-S4, pH_stat method, “Schweizer method” (elution test, Switzerland), and some variants of the pH_stat method on two very different samples are described. A rudimental sediment and a municipal sewage sludge are chosen as sample materials. The metal contents of extract solutions are determined by ICP-OES. The results of the DIN-S4 extractions depend definitely on the mechanic way of movement, i.e. the amount of heavy metals which are mobilized out of the samples differs considerably. In fact, DIN-S7 in combination with DIN-S4 is not sufficient to estimate the mobility of heavy metals. Solid samples should only be evaluated by applying a combination of several methods of extraction. The usefulness of the pH_stat method for an evaluation is discussed.     

Preparative isolation and characterization of heavy metal complexes from acid mine drainage and surface wastewater

A preparative method was developed to sample dissolved organic carbon (DOC) and heavy metals (Ni, Mn) from polluted surface waters. Main focus was set on the preparative production of freeze‐dried samples mainly composed of organic ligands from heavy metal complexes. First characterizations were done in the aqueous phase. Finally, freeze‐dried samples provide stable organic matter for multiple characterizations. Acid mine drainage of the former mining area of Ronneburg (Germany) hold elevated concentrations of heavy metals and low concentrations of DOC. Municipal wastewater, passing the spoil pile, held elevated concentrations of DOC and low concentrations of heavy metals. Dissolved components smaller than 0.45 μm and larger than 1 nm were concentrated by nanofiltration. Organic heavy metal complexes were isolated from this solution by size‐exclusion chromatography (SEC). Different size classes of molecules were collected from the column effluent, depending on their elution time, and were characterized by UV spectroscopy, ICP‐OES, and DOC measurements. All samples held organic heavy metal compounds with different retention times. The organic heavy metal complexes in acid mine drainage had higher retention times than complexes from municipal wastewater. Most interestingly, we found different affinities of heavy metals to different size classes of DOC. This affinity of the heavy metals differs with size and origin of the DOC.     

Kurzzeitermittlung der Ablaufqualität von Belebtschlammanlagen anhand der Atmungsaktivität

For checking the quality of the effluent from an activated sludge plant for waste-waters from the sulphite pulp production the respiration of an activated sludge sample in air-saturated water is determined initially without the addition of substrate (ground respiration) and after that with an addition of substrate (methanol, substrate respiration) by means of the Clark-electrode. The measuring device is designed by means of zero displacement in such a way that the difference of the oxygen concentration is indicated by a time relay as the difference quotient. Between the ground respiration and the effluent concentration of BOD₅ exists a significant positive regression, which can be used for controlling the plant. The determination of the substrate respiration serves only for checking with respect to perhaps given inhibition of the conversion of matter by the activated sludge. The determination of the activity of the activated sludge sample takes only 20 min; inclusive of the required determination of the dry matter of sludge, the technique provides a well reproducible measured value for the biochemical conversion in the activated sludge plant within 1… 1.5 h.     

Self-organizing map for the detection of seasonal variations in Sidi Chahed Dam sediments (Northern Morocco)

ABSTRACT

A database of 88 superficial sediment samples, distributed in space and time, was collected from the Sidi Chahed Dam (northeast of Meknes city, Morocco) and from four other reference stations (in the same region) located in supposedly uncontaminated environments. Analyses were focused on the physico-chemical characteristics and concentrations of heavy metals (Fe, Mn, As, Cu, Zn, Pb, Cr, Cd). The database was processed by advanced statistical analysis techniques. The method of classification by self-organizing maps (SOM) was used, permitting understanding and visualization of the spatial and temporal distribution of samples. Principal component analysis (PCA) and SOM hierarchical classification (SOM-HC) were used to validate the classification and detect seasonal variations in heavy metal concentrations. Dependencies between different metal tracers were considered and their spatio-temporal distribution is shown, together with the ranking of clusters, according to their pollution levels. Thus, autumn samples were the only ones with high concentrations of As, compared to the four reference stations. This is due to leaching of bare soil by the first stormy rains of autumn. In winter and spring samples, the concentrations of tracers Mn, Zn, Cu, Pb, Cd and Cr were relatively high compared to those of the reference stations. Summer sample concentrations were most comparable with the reference stations, probably due to the scarcity of rainfall and runoff in this season.

Editor Z.W. Kundzewicz Associate editor E. Gargouri     

A Screening Procedure for Heavy Metals in Soil Extracts by Alcohol Dehydrogenase and Urease Inhibition Eine Screening-Methode für Schwermetalle in Extrakten aus Bodenproben,basierend auf der Inhibierung der Enzyme Alkoholdehydrogenase und Urease

A screening method for heavy metals in aqueous extracts of soil is presented which is based on inhibition of the enzymes urease and alcohol dehydrogenase. The method is suitable to detect cupric and mercury ions in concentrations below 0.01 mg/L and several other heavy metal ions in 1000 fold higher concentration. It is shown that the test may be used for screening of mercury ion concentrations exceeding 0.03 mg/L in aqueous solution when copper chelators are added to the test system. The usefulness of the presented tests to detect heavy metals eluted from soil was verified with samples from ore mining waste. The concentration of copper, lead, and zinc eluted from these samples to different amount was determined by atomic absorption spectrometry and was in good agreement with the enzyme inhibition data obtained with these samples.     

Porosity measurement of heavy oil sands

Porosity measurement is an important step for petrophysical characterization of reservoir rocks, as porosity is essential for analysing elastic properties and estimating the capacity of rocks to hold hydrocarbon resources. Commonly used porosity measurement methods fail to work on heavy oil sands, because of the loose fragile sand frame and solid-like irreducible heavy oil. We develop three methods to measure the porosity of heavy oil sands, which are feasible and affordable in most laboratories. Method 1 involves calculating the bulk volume of the sample by measuring its physical dimensions directly. Method 2 uses calibrated sample weight and volume (after removing the protecting foil cover and metal clips). Method 3 first applies pressurizing on samples and then measures the weight and volume of the bare samples. The measurement results of the three methods are then compared and method 3 is determined as the most reliable, which is also verified by the porosity log. Finally, an analysis of the potential sources of errors associated with method 3 is performed.     

Indicator Tissues for Heavy Metal Monitoring – Additional Attributes

Preferred characteristics of biological indicators for heavy metal monitoring in marine ecosystems were documented 30 years ago. Heavy metal data from Raine Island on the outer-northern Great Barrier Reef are presented to introduce additional attributes for consideration, including a widened choice of biological tissues due to advances in trace heavy metal analysis. Kidney tissues, visceral mass and adductor muscle from the giant clam (Tridacna maxima), muscle tissue from trochus (Trochus niloticus) and axial muscle from four species of fish were targeted. The kidneys of giant clams had concentrations of heavy metals from 2 (Zn) to 2780 (Ni) times higher than corresponding concentrations in adductor muscles. Also, tissues of giant clam and the muscle of trochus gave different signals with respect to bio-available heavy metals. Linear correlations for heavy metals within and between tissues of giant clam and within muscle tissue of trochus, offer opportunities for the use of surrogates as well as a possible mathematical basis for assessing trends in heavy metal pollution.     

Untersuchungen zum Schadstoffpotential von Wasserwerksschlämmen

Investigation on the Pollution Potential of Waterworks Sludges Several contaminated sludges from water treatment plants with known or estimated concentrations of trace elements were investigated for their leaching characteristics and long-term stability using standard and advanced test procedures. Potentially hazardous elements in the sludge are zinc, nickel, and arsenic with concentrations of up to 1.2 g/kg dry matter (mass). Preliminary sorption tests with synthetic sludge components like iron hydroxide, manganese oxide, silicate clay minerals, and chitine powder as a model organic component showed that Cu is associated with the organic phase wheras arsenic is predominantly bound to the iron oxide minerals. The recently suggested pH_stat test procedure was used to assess the leaching characteristics of metals at typical pH values. This procedure was compared with the DEV-S4 test, the current standard test in Germany, consisting of a simple lixiviation of the solids with water, without pH control. The pH_stat test yields results which are much better to interprete than those obtained by the DEV-S4 procedure. The iron and manganese sludges are well buffered against changes in pH and redox potential so that low pH values and/or reducing conditions can hardly occur. Thus, in deposited material a sudden leaching of heavy metals is unlikely and due to the presence of iron and manganese oxides the pentavalent arsenic is protected against conversion into the highly mobile trivalent form at neutral to low pH. Co-deposition with reducing organic matter and alkaline stabilisation material or waste (like fly ash) could influence the binding properties and should be strictly avoided.     

Dimethylsulfoxidreduktase-Aktivität Charakterisierung der mikrobiellen Biomasseaktivität im Schlamm einer belüfteten Abwasserteichanlage

Dimethyl Sulfoxide Reduction Method for the Characterization of Biomass Activity in Sludge of an Aerated Lagoon The microbial biomass activity was studied in sludge from a wastewater lagoon (Hatzbachtal) which consisted of 4 aerated ponds and one polishing pond. The lagoon was characterized by low BOD₅ loading and high dilution because of water from the surroundings. Sludge samples were taken from 4 sampling sites of each aerated pond and from one site of the polishing pond. The biomass activity in the sludge samples was analysed with the help of dimethyl sulfoxide reductase (DRA) and dehydrogenase (DHA) activity. In addition, C_org-content was also determined. The effect of different reaction parameters on the DRA was studied in relation to incubation period, temperature and atmosphere as well as sludge weight and pH value. The results presented here show that a linear increase in the DRA occured for the sludge weight ranging from 0.1 to 0.5 g, incubation period from 0.5 to 11 h and incubation temperature from 20 to 50 °C. The pH spectrum from acidic to neutral did not effect the DMS formation in sludge. Although the values for DRA were always higher in anaerobic incubation of sludge than in aerobic incubation, the courses of the DRA in both conditions were parallel. Comparing the biomass activity in sludge from different sampling sites of the aerated ponds, the average C_org-content was found to be reflected by the DRA and DHA. Further, the variation in the DRA could represent also the influence of oxygen concentration. Therefore, a reduction in biomass activities indicated a decline in the availability of oxygen.     

Heavy metal concentrations in growth bands of corals: a record of mine tailings input through time (Marinduque Island,Philippines)

The impact of copper mining along the western coast of Marinduque Island was investigated. Historic input of mine tailings in the coastal region was traced through variations in heavy metal concentrations in Porites growth bands. Five samples were collected from three reefs showing different modes and extent of exposure to mine tailings. Baseline metal concentrations in Porites were established using a coral from a reef that is least exposed to contamination. The lowest mean values of Cu (0.7 microg/g), Mn (0.8 microg/g), and Zn (1.0 microg/g) were calculated from annual skeletal bands representing five years of growth. Conversely, a sample from a reef adjacent to an old tailings stockpile displayed consistently elevated metal values in its growth bands. Mean Cu, Mn, and Zn values for this coral are 3.1, 1.0 and 1.8 microg/g, respectively. Corals from the Ihatub reef showed a distinct metal concentration peak in their 1996 growth ring. These peaks coincide with a documented release of mine tailings in the Ihatub area during that year. Other metal peaks observed in coral samples correlate with years of high precipitation which may have resulted in increased sediment transport in the region. The metals are presumed to be mostly bound to the aragonite lattice of the coral skeleton, however, contribution from incorporated detrital materials to the observed metal signal (mainly of Fe) could not be easily discounted.     

Bestimmung der Aktivität von Belebtschlamm über die Geschwindigkeit der Biosynthese von Aminopeptidasen

The authors describe a possibility of a fast determination of the metabolic activity of various activated sludge samples. There is not used the sludge property of digestion, but the biosynthesis of aminopeptidases. Egg albumin has been found to be the optimum standard indicator. The activity of the investigated activated sludge is derived from the rate of the biosynthesis of aminopeptidases. The technique proposed can be used also for determining the toxic effects of different substances on activated sludge.     

Paddy soil — A suitable target for monitoring heavy metal pollution by magnetic proxies

A preliminary magnetic study around Meishan steel mill in Nanjing (SE China) was carried out combining geochemical analysis with scanning electron microscopy (SEM) to prove that paddy soil can be a suitable target for environmental study on heavy metal pollution. Magnetic background investigation showed a strong variation in this area due to different land uses and soil types. Magnetic susceptibilities (MS) measured on forest soils are much higher than in paddy fields, and values below 20 cm of the soil surface in forest with parent material of Xiashu loess are several times higher than in paddy soil with parent material of fluvisol. Measurements on vertical profiles show that paddy soil has a very low and stable magnetic background with mass-specific MS around 15 × 10^{− 8} m³ kg^{− 1}. A strong enhancement of MS values is found in the upper ~ 20 cm of paddy soil predominated by multidomain and pseudo single domain magnetite. However, relatively low S-ratios (0.57 to 0.85) reveal a significant contribution of imperfect anti-ferromagnetic minerals. Detailed research on a paddy soil core at site C719 near the steel mill indicates strong correlation between magnetic mineral concentration-related parameters (χ, ARM, SIRM) and heavy metal concentrations of Cu, Pb and Zn. In addition, typical anthropogenic Fe-spherules are detected in top paddy soil by means of SEM, which indicates that the increase of susceptibility in upper soil is mainly caused by steel mill emission. Mapping of MS in paddy fields across the steel mill area shows a decrease of MS with the distance to the major emission zone. Positive correlation between χ and Zn is found by measuring surface soil samples around the steel mill. Because of low background and high homogeneity of the ~ 20 cm uppermost mixing layer paddy fields are especially suitable for magnetic surface mapping of heavy metal pollution.     

Cd(II), Pb(II) and Zn(II) Removal from Contaminated Water by Biosorption Using Activated Sludge Biomass

Biosorption using activated sludge biomass (ASB) as a potentially sustainable technology for the treatment of wastewater containing different metal ions (Cd(II), Pb(II) and Zn(II)) was investigated. ASB metal uptake clearly competed with protons consumed by microbial biomass compared with control tests with non‐activated sludge biomass. Biosorption tests confirmed maximum exchange between metal ions and protons at pH 2.0–4.5. It was revealed by the study that the amount of metal ions released from the biomass increased with biomass sludge concentration. The result showed that maximum absorption of metal ions was observed for Cd(II) at pH 3.5, Pb(II) at pH 4.0, and pH 4.5 for Zn(II) ions. The maximum absorption capacities of ASB for Cd(II), Pb(II) and Zn(II) were determined to be 59.3, 68.5 and 86.5%, respectively. The biosorption of heavy metals was directly proportional to ASB stabilization corresponding to a reduction in heavy metals in the order of Cd < Pb < Zn. The order of increase of biosorption of metal ions in ASB was Zn(II) < Pb(II) < Cd(II), and this was opposite to that of non active sludge. The results indicate that ASB is a sustainable tools for the bioremediation of Cd(II), Pb(II) and Zn(II) ions from industrial sludge and wastewater treatment plants.     

Polarographische Bestimmung von Schwermetallen im Klärschlamm

The differential-pulse polarography (DPP) and the stripping voltametry (SV) are investigated in detail with respect to their suitability for the quantitative detection of individual traces of heavy metals in sewage sludge. The results are checked on the basis of AAS analyses and by the standard-addition method. From the hydrochloric-acid extracts of fused sludge samples down to 1 μg/l can be detected by the SV, whereas the DPP reaches a sensitivity of 100 μg/l. The following basic electrolytes are used: Zn: 2 … 3 mol/l H₃PO₄; Cu: 0.4 mol/l K₂CO₃, 0.2 mol/l Na-K-tartrate, 0.1 mol/l HCl; Ni: 1 mol/l NH₄OH, 1 mol/l NH₄Cl, 25 ml/l triethylamine; Pb and Cd: 0.1 … 0.2 mol/l HCl.     

Kurzzeit-Toxizitätstests zur Messung der Toxizität von Chemikalien gegenüber Belebtschlamm

Short-term Toxicity Tests for the Measurement of Toxicity of Chemicals Towards Activated Sludge. To avoid severe damage to the activated sludge of a wastewater treatment plant it is necessary to control the sludge activity by means of biological test systems. Especially the short-term respiration assay and the dehydrogenase assay with resazurin as a redox-dye seem to be appropriate for this monitoring program. The practical performance of both test systems was optimized in some essential points. With the help of several reference substances both monitoring systems were tested for practical use as short-term toxicity tests. The results of the investigations showed that the inhibitory concentrations measured in both test systems were partially very different. In monitoring experiments with laboratory-scale wastewater treatment plants it could be shown that a positive correlation between respiration activity and dehydrogenase activity is not always given. Furthermore, a pH-dependent toxicity could be demonstrated for several substituted phenols.     

Zum Einfluß des pH-Wertes und des Calciumgehaltes auf Metall-Fulvinsäure-Bindungen — Inversvoltammetrische und chemometrische Untersuchungen

The Influence of pH and Calcium Concentration on Metal-Fulvic Acid Bonds – Stripping Voltammetric and Chemometric Investigations. Electrochemically available metal concentrations of Cd, Cu and Zn were analyzed in dependence of different concentrations of calcium, fulvic acids and pH by Differential Pulse Anodic Stripping Voltammetry (DPASV). A statistical experimental design was the base to minimize the number of experiments and to include the multifarious interactions between the independent variables (Ca concentration, concentration of fulvic acids and the pH value) and otherwise the electrochemically available metal concentrations of Cd, Cu and Zn. At first analysis of experimental data was carried out by multiple linear regression. The main influence on available metal concentrations is the pH value especially for Cu. The Ca ion influence has not competitive effect and is only significant for Cd and Cu. It has an effect on the metal-fulvic acid-bonds. Two factor interactions exist for pH/fulvic acids and for Ca/fulvic acids too. The partial least squares regression (PLS) model was used to include the interactions between the metals Cd, Cu and Zn. For proving these two models the three parameters pH, Ca and fulvic acid were varied within the calibration range of the models and predicted values were compared with the experimental values. The approach with the PLS model is better than the approach with the multiple linear regression (normally used mathematical method of analysis of a factorial plan) with a relative error of 9.7% for modelling of Cd, 6.0% for Zn and 58% for Cu in relation to multiple linear regression with errors of 12% for Cd, 8.6% for Zn and 65% for Cu. The PLS modelling is a suited tool for modelling chemical interactions also in simulated natural matrices.     

基于筛分水平浓度法的洞庭湖沉积物质量基准初步分析

基于2013 2015年调查获取的129个洞庭湖表层沉积物和底栖生物的调查数据,应用筛分水平浓度法初步探讨了洞庭湖沉积物几种重金属沉积物质量基准的推荐值.结果表明,洞庭湖沉积物砷(As)、镉(Cd)、铬(Cr)、铜(Cu)、铅(Pb)和锌(Zn)含量均值为17.2、2.63、56.9、32.4、38.4和96.3 mg/kg(DW);筛分水平浓度法获取的洞庭湖沉积物As、Cd、Cr、Cu、Pb和Zn质量基准分别为11.97、1.13、42.03、19.17、23.63和67.54 mg/kg(DW).通过与不同国家及地区指定的重金属质量基准推荐值以及本地区采用其他方法推导的重金属基准推荐值进行比较,推算出本研究获取的6种重金属沉积物质量基准推荐值接近所有数据的中间值.对于洞庭湖流域,不同方法获取的沉积物重金属质量基准具有可比性.然而,鉴于用于推导沉积物质量基准的数据采集涉及的区域较为有限,且除了重金属污染外,影响底栖生物分布的因素较为复杂,导致获取的沉积物重金属质量基准推荐值存在一定的不确定性.     

Das Entwässerungsverhalten von Klärschlamm in Gegenwart von Polyelektrolyten

Dewatering Behaviour of Sludge in the Presence of Polyelectrolytes Interactions of sludge particles with well defined synthetic polyelectrolytes of different charge, molecular mass, and molecular geometry were investigated by means of zeta- and streaming potential measurements and polyelectrolyte titrations. Different mechanisms of flocculation were discussed with regard to the dewatering behaviour of the sludge. In dependence on the flocculation procedure (cationic monoflocculation, anionic-cationic, and cationicanionic dual flocculation) as well as on the chain length and branching of the polyelectrolytes used, different mechanisms of sludge dewatering were discussed: Polyanions are not adsorbed on the sludge particles and lead to a decline of the dewatering results. Linear short chain polycations result in a flocculation after surface charge neutralization of the particles according to a patch mechanism. Long chain linear polycations cause a bridging of the particles leading to a flocculation without charge neutralization of the aggregates formed. With branched polycations, a flocculation according to a patch mechanism is observed. These polycations form sludge particle aggregates which are surface charge neutralized at the flocculation point. In anionic-cationic dual flocculations using long chain polycations, an inclusion flocculation due to polyanion-polycation complex formation is the predominating mechanism. The cationic-anionic dual flocculation with complete covering of the particles with polycations in the first step can be discussed by a patch mechanism quite similar to an anionic monoflocculation of cationic particles. By knowing the mechanism of interaction for a given flocculation agent, an optimal sludge dewatering procedure can be predicted.     

Bioavailability of heavy metals in soil of the Tieguanyin tea garden,southeastern China

The bioavailability of 22 heavy metals was investigated at 19 sampling sites in Tieguanyin tea garden in Anxi County,Fujian Province,southeastern China.Heavy metal concentrations were determined by inductively coupled plasma-mass spectrometry(ICP-MS)and evaluated by geo-accumulation index(I_(geo)).Dilute nitric acid extraction was used to evaluate biological activity.Cu,Pb,and Cd were highly bioavailable and most easily absorbed by tea trees.Heavy metal bioavailability in the surface soil was as the ratio of the effective state to the total amount.Cd had the highest I_(geo)values,and the respective samples and sites were classified as moderately/strongly contaminated.Cd element is considered the main factor of heavy metal pollution in the tea garden in Anxi.The other heavy metals studied were present in lower concentrations;thus,the samples were classified as uncontaminated or slightly contaminated.     

Comprehensive assessment of heavy metal contamination in sediment of the Pearl River Estuary and adjacent shelf

Total metal concentrations (Cr, Ni, Cu, Zn, and Pb), acid volatile sulfide and simultaneously extracted metals (AVS-SEM), and heavy metal fractionation were used to assess the heavy metals contamination status and ecological risk in the sediments of the Pearl River Estuary (PRE) and adjacent shelf. Elevated concentrations at estuarine sites and lower concentrations at adjacent shelf sites are observed, especially for Cu and Zn. Within the PRE, the concentration of heavy metals in the western shore was mostly higher than that in the middle shore. The metals from anthropogenic sources mainly occur in the labile fraction and may be taken up by organisms as the environmental parameters change. A combination of total metal concentrations, metal contamination index and sequential extraction analysis is necessary to get the comprehensive information on the baseline, anthropogenic discharge and bioavailability of heavy metals.