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.     

Study of Metal Distribution in Raw and Screened Swine Manure

The growth of industrial swine production over the last few years has led to a growth in concern over effluents generated by the activity. Several elements, mainly toxic metals, can be present in swine wastewater and can have a serious environmental impact. It is important, therefore, to know the metal concentration before the discharge of wastewater. In this work the temporal metal distribution in swine manure and its potential reduction using coarse (2 mm) and fine (<0.45 μm) liquid‐solid separation techniques were investigated. In order to do this, different swine manure sample preparation methods for Al, Ba, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Sr and Zn determination by Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES) were tested. The acid mixtures used to digest the manure sample significantly affected the metal recovery. Good analyte recoveries were observed with nitric acid/hydrogen peroxide mixtures or nitric acid/perchloric acid mixtures. Sulfuric acid/hydrogen peroxide mixtures produced inconsistent results and poor recoveries, mainly for Ba and Pb. It was observed that metal concentrations in swine manure varied greatly with time, up to one order of magnitude, due to changes in swine production such as feed and animal numbers. Metals concentrations observed in the raw wastewater exceeded Brazilian limits for discharge into water bodies and recommendations for agricultural use. Results obtained from the liquid‐solid separation study showed that metals in the raw swine manure were not removed with coarse screening. However, the major fraction of metals were removed by filtration (0.45 μm), with the exception of Na, K and Sr. Thus, the use of liquid‐solid separation techniques that capture the fine solid fractions (and associated metals) from raw manure can have a favorable impact on the environment and contribute to swine production wastewater treatment.     

Dissolved and particulate trace metals in meltwater from the Rhône glacier

Glacial meltwater and sediment at the source of the River Rhône have been analyzed to determine: 1. the partitioning of Al, Cd, Co, Cu, Cr. Fe, Mn, Ni, Pb and Zn between the water and particulate phase. 2. the particle size ranges which affect the dissolved trace metal ion composition of the meltwater and 3. the availability (potential release) of the ten trace metal ions from the sediment. Greater than 80% of the total Cd, Cu, Mn, Ni and Zn were found to be in operationally-defined (0.4 μm) dissolved forms. Fe and Al in the meltwater are primarily associated with particles in the size range 0.4–8 μm, while Cd. Cu, Mn, Ni and Zn occur with particles smaller than 0.1 μm. For the sediment, Cu, Ni and Pb were significantly present as exchangeable forms; only Cu, Ni, Pb and Zn were determined as organicallybound forms.     

Fractionation of Ni,Cr and Cu from Soil by Sequential Extraction Procedure and Determination by Inductively Coupled Plasma Optical Emission Spectrometry

Five‐step sequential extractions were employed to fractionation of Ni, Cr and Cu in soil polluted by anthropogenic activities and determine the mobility of the metals. Twelve samples were collected on an agricultural area that was located near an airport and intercity roads in Elazig‐Turkey. Exchangeable, organically bounded, carbonate bounded, adsorbed species on Fe and Mn oxides and residual species (except silicates) of Ni, Cr and Cu were extracted into solution by using CaCl₂, Na₄P₂O₇, Na₂EDTA, NH₂OH–HCl and HNO₃–H₂O₂, respectively. Mobile metal concentrations in fractions and total recoverable in soils were determined by using inductively coupled plasma‐optical emission spectrometry (ICP‐OES). Total recoverable Ni, Cr and Cu concentrations were in the range of 40–119, 45–126 and 23–72 mg kg^?1, respectively. It was observed that total concentrations of metals in some of the samples were higher than the permitted values. The sum of the mobile percentages of metals was found to be lower than 50%. The Ni, Cr and Cu percentages for exchangeable species are in the ranges of 0.18–1.64, 0.03–0.59 and 0.42–2.53%, respectively.     

Development of Bench‐Scale Bio‐Packed Column for Wastewater Treatment from Optical Emission Spectrometry

An eco‐friendly and inexpensive technique for wastewater treatment originated from inductively coupled plasma‐optical emission spectrometry (ICP‐OES) is presented within this paper. The proposed process comprised of loading waste crab shells in packed column for adsorption of heavy metal ions, followed by desorption using 0.01 M HCl. An exhaustive physical and chemical characterization of ICP‐OES wastewater revealed the complex nature of effluent, including the presence of 15 different metals and metalloid under strong acidic condition (pH 1.3). Based on the preliminary batch experiments, it was identified that solution pH played a major role in metal sequestration by crab shell with pH 3.5 identified as optimum pH. Rapid metal biosorption kinetics along with complete desorption and subsequent reuse for three cycles was possible with crab shell‐based treatment process. Continuous flow‐through column experiments confirmed the high performance of crab shell towards multiple metal ions with the column able to operate for 22 h at a flow rate of 10 mL/min before outlet concentration of arsenic reached 0.25 times of its inlet concentration. Other metal ions such as Cu, Cd, Co, Cr, Pb, Ni, Zn, Mn, Al, and Fe were only in trace levels in the treated water until 22 h. The performance of the treatment process was compared with trade effluent discharge standards, and the process flow diagram along with cost analysis was suggested.     

Alkaline Degradation of Dissolved Organic Matter

The degradation of dissolved organic matter (DOM) was studied in alkaline solution. The products were characterised using UV/vis spectroscopy, size‐exclusion chromatography (SEC), and by the analysis of low‐molecular‐weight organic acids (LMWOA). The degradation experiments were performed with water from a brown water lake or its isolated fulvic acid fraction and sodium hydroxide at different reaction times and temperatures. Depending on the wavelength and the reaction time, the UV/vis absorbance between 230 nm and 600 nm increased or decreased. The behaviour of model compounds during reactions in alkaline media was compared to the UV/vis spectroscopic behaviour of DOM. The release of LMWOA was described by kinetic data and compared to the data of model reactions. Evidence was given for the carboxylic esters playing a significant role in the release of LMWOA only during the beginning of the alkaline degradation. The results gained by SEC with on‐line UV and DOC detection showed that the average size of DOM was decreasing, and that a major part of the degradation products consisted of low‐molecular‐weight mono‐ and dicarboxylic acids.     

Determination of Cu,Fe, and Ni in Spices after Preconcentration on Diaion‐HP 20 Resin as Their Zincon Complexes

In this work, a new separation–preconcentration method was developed for the determination of trace amounts of Cu(II), Ni(II), and Fe(III) by flame atomic absorption spectrometry (FAAS). Analytes were complexed by using zincon (2‐[2‐[alpha(2‐hydroxy‐5‐sulfophenylazo) benzylidene] hydrazino] benzoic acid sodium salt). The analyte ions were quantitatively adsorbed on a Diaion HP‐20 resin at pH 5. The retained metal ions on the resin were eluted by acetone. The analytical parameters such as pH of the sample, eluent type and volume, sample volume, and flow rates of the solution and the eluent were investigated. The influences of concomitant ions on the recoveries of the analytes were also examined. The instrumental detection limits for the analytes after application of the presented solid‐phase extraction procedure were in the range of 0.72–1.41 µg/L. The validation of the presented procedure was checked by analyzing certified reference material of SRM1515 Apple Leaves. The procedure was performed by analyzing some spice samples.     

Use of the Anion‐Exchange Resin Amberlite IRA‐93 for the Separation of Arsenite and Arsenate in Aqueous Samples

The method described uses the separation of As(III) and As(V) species in aqueous samples by means of the anion‐exchange resin Amberlite IRA‐93. The samples were acidified using acetic acid and passed through a glass column filled with pre‐treated Amberlite IRA‐93 resin. As(III) was poorly adsorbed on the anionic exchanger material, whereas As(V) was retained. The arsenic concentration was measured in the column effluent by graphite furnace AAS (GF‐AAS). The retained As(V) was eluted from the column using 1 M NaOH. Prior to the determination of the As(V) concentration in the NaOH eluate, the eluate was passed through a glass column filled with a cation‐exchange resin (Amberlite 200) to remove sodium ions and minimize the Na⁺ interference with the AAS determination. After calibration the method was applied to the separation of As(III) and As(V) species in two aqueous extracts of arsenic contaminated soils. The results were compared with those obtained from an on‐line separation and determination of As(III) and As(V) in the aqueous soil extracts using a state of the art HPLC‐ICP‐MS system.     

Preconcentration by Coprecipitation of Copper and Nickel with Mo(VI)/Triazole Derivative System and Their Determinations by Flame Atomic Absorption Spectrometry in Food and Water Samples

A new separation and preconcentration technique based on coprecipitation of Cu(II) and Ni(II) ions by the aid of Mo(VI)/di‐tert‐butyl{methylenebis[5‐(chlorobenzyl)‐4H‐1,2,4‐triazol‐3,4‐diyl]}biscarbamate (BUMECTAC) precipitate has been established. The Mo(VI)/BUMECTAC precipitate was dissolved by concentrated HNO₃ and the solution was completed to 5.0 mL with distilled/deionized water. The levels of the analyte ions were determined by flame atomic absorption spectrometer. The effects of experimental conditions like HNO₃ concentration, amount of BUMECTAC and Mo(VI), sample volume, etc. and also the influences of some foreign ions were investigated in detail on the quantitative recoveries of analyte ions. The preconcentration factors were found to be 40 for Cu(II) and 100 for Ni(II) ions. The detection limits for Cu(II) and Ni(II) ions based on 3σ (N:10) were 0.43 and 0.70 µg L^?1, respectively. The relative standard deviations were found to be lower than 4.0% for both analyte ions. The accuracy of the method was checked by spiked/recovery tests and the analysis of two certified reference materials (Environment Canada TM‐25.3 and CRM‐SA‐C Sandy Soil C). The procedure was successfully applied to sea water and stream water as liquid samples and baby food as solid sample in order to determine the levels of Cu(II) and Ni(II) ions.     

Provenance of long‐travelled dust determined with ultra‐trace‐element composition: a pilot study with samples from New Zealand glaciers

We report high‐precision inductively coupled plasma mass spectrometric (ICP‐MS) compositional data for 39 trace elements in a variety of dust deposits, trapped sediments and surface samples from New Zealand and Australia. Dusts collected from the surface of alpine glaciers in the Southern Alps, New Zealand, believed to have undergone long‐distance atmospheric transport from Australia, are recognizable on account of their overabundances of Pb and Cu with respect to typical upper crustal values. Long‐travelled dust from Australia therefore scavenges these and other metals (e.g. Zn, Sb and Cd) from the atmosphere during transport and deposition. Hence, due to anthropogenic pollution, long‐travelled Australian dusts can be recognized by elevated metal contents. The relative abundance of 25 other elements that are not affected by atmospheric pollution, mineral sorting (Zr and Hf) and weathering[sol ]solubility (alkali and earth alkali elements) reflects the geochemistry of the dust source sediment. As a result, we are able to establish the provenance of dust using ultra‐trace‐element chemistry at regional scale. Comparison of long‐travelled dust chemistry with potential Australian sources shows that fits of variable quality are obtained. We propose that the best fitting potential source chemistry most likely represents the major dust source area. A binary mixing model is used to demonstrate that admixture of small quantities of local dust provides an even better fitting dust chemistry for the long‐travelled dusts. Copyright © 2005 John Wiley & Sons, Ltd.     

The effect of an oil drilling operation on the trace metal concentrations in offshore bottom sediments of the Campos Basin oil field,SE Brazil

The concentrations of Al, Fe, Mn, Zn, Cu, Pb, Ni, Cr, Ba, V, Sn and As in offshore bottom sediments from the Bacia de Campos oil field, SE Brazil, were measured at the beginning and at 7 months after completion of the drilling operation. Concentrations of Al, Fe, Ba, Cr, Ni and Zn were significantly higher closer to the drilling site compared to stations far from the site. Average concentrations of Al, Cu, and in particular of Ni, were significantly higher at the end of the drilling operation than at the beginning. Comparison between drilling area sediments with control sediments of the continental platform, however, showed no significant difference in trace metal concentrations. Under the operation conditions of this drilling event, the results show that while changes in some trace metal concentrations do occur during drilling operations, they are not significantly large to be distinguished from natural variability of the local background concentrations.     

Selective Separation and Preconcentration of Fe(III) and Zn(II) Ions by Solvent Extraction Using a New Triketone Reagent

A simple, rapid, and accurate method was developed for separation and preconcentration of trace levels of iron(III) and zinc(II) ions in environmental samples. Methyl‐2‐(4‐methoxy‐benzoyl)‐3‐(4‐methoxyphenyl)‐3‐oxopropanoylcarbamate (MMPC) has been proposed as a new complexing agent for Fe(III) and Zn(II) ions using solvent extraction prior to their determination by flame atomic absorption spectrometry (FAAS). Fe(III) and Zn(II) ions can be selectively separated from Fe(II), Pb(II), Co(II), Cu(II), Mn(II), Cr(III), Ni(II), Cd(II), Ag(I), Au(III), Pd(II), Cr(VI), and Al(III) ions in the solution by using the MMPC reagent. The analytical parameters such as pH, sample volume, shaking time, amount of MMPC reagent, volume of methyl isobutyl ketone (MIBK), effect of ionic strength, and type of back extractant were investigated. The recovery values for Fe(III) and Zn(II) ions were greater than 95% and the detection limits for Fe(III) and Zn(II) ions were 0.26 and 0.32 µg L^?1, respectively. The precision of the method as the relative standard deviation changed between 1.8 and 2.1%. Calibration curves have a determination coefficient (r²) of at least 0.997 or higher. The preconcentration factor was found to be 100. Accuracy of the method was checked by analyzing of a certified reference material and spiked samples. The developed method was applied to several matrices such as water, hair, and food samples.     

Evaluation of metal contamination in coastal sediments of the Bay of Bengal, India: geochemical and statistical approaches

Surface sediment samples collected from the inner shelf region of the Bay of Bengal, were analysed for the major elements and total and acetic acid available trace elements (Al, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, Si, Zn) to evaluate geochemical processes influencing their distribution. Major elemental analysis showed that the sediments had high concentrations of Si and relatively low concentrations of Al and Fe. Both major elemental and trace metal concentrations indicated that the sediments represent weathered products of granite and charnockite. Normalization of metals to Al indicated relatively high enrichment factors for Pb, Cd, Zn and Cr. The higher proportions of nondetrital Pb (66%), Cd (41%) and Co (28%) reveal metal contamination due to anthropogenic inputs. Factor analysis (FA) identified six possible types of sedimentological and geochemical associations. The dominant factor accounting for 26.9% of the total variance identifies an anthropogenic input and accumulation of nondetrital Cd, Co, Cr, Ni and Pb. Association of these metals with CaCO3 reveals that shell fragments in the surface sediments are likely act as a carrier phase for nondetrital metals. The results are discussed in the context of the sources and pathways of elements in the Bay of Bengal.     

Geochemical Distribution of Trace Elements in Groundwater from the North Mara Large‐Scale Gold Mining Area of Tanzania

The influence of large‐scale mining operations on groundwater quality was investigated in this study. Trace element concentrations in groundwater samples from the North Mara mining area of northern Tanzania were analyzed. Statistical analyses for relationships between elemental concentrations in the samples and distance of a sampling site from the mine tailings dam were also conducted. Eleven trace elements (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) were determined, and averages of Fe and Al concentrations were higher than levels accepted by the Tanzanian drinking water guideline. Levels of Pb in three samples were higher than the World Health Organization (WHO) and United States Environmental Protection Agency (USEPA) drinking water guidelines of 10 and 15 µg/L, respectively. One sample contained a higher As level than the WHO and USEPA guideline of 10 µg/L. The correlation between element concentrations and distance from the mine tailings dam was examined using the hierarchical agglomeration cluster analysis method. A significant difference in the elemental concentration existed depending on the distance from the mine tailings dam. Mann–Whitney U‐test post hoc analysis confirmed a relationship between element concentration and distance of a sampling site from the mine tailings dam. This relationship raises concerns about the increased risks of trace elements to people and ecosystem health. A metal pollution index also suggested a relationship between elemental concentrations in the groundwater and the sampling sites’ proximity from the mine tailings dam.     

Organically Bound Nutrients in Dissolved Organic Matter Fractions in Seepage and Pore Water of Weakly Developed Forest Soils

Previous field and laboratory studies showed that organically bound nutrients can contribute largely to the export of N, P, and S from soil into aquatic systems. One possible determinant for the losses of dissolved organic nutrients leaving the soil environment could be their distribution between dissolved organic matter (DOM) fractions of different mobility in soil. To elucidate the potential influence of DOM fractions under varying flow conditions on the vertical translocation of organically bound nutrients, we determined the concentrations and fluxes of dissolved organic C (DOC) and nutrients (DON, DOP, DOS) in soil water under a Scots pine (Pinus sylvestris L.) and a European beech (Fagus sylvatica L.) forest. We sampled seepage water from the organic forest floor layer and the mineral subsoil using zero‐tension lysimeters and soil pore water using tension lysimeters and suction cups. DOM in soil water was fractionated into hydrophilic and hydrophobic compounds by XAD‐8 at pH 2. We found that the organic forest floor layers were large sources for DOC, DON, DOP, and DOS. The dissolved organic nutrients were mainly concentrated in the hydrophilic DOM fraction which proved to be more mobile in mineral soil pore water than the hydrophobic one. Consequently, the concentrations and fluxes of dissolved organic nutrients decreased less with depth than those of DOC. Concentrations as well as fluxes in subsoil pore water of DOC and dissolved organic nutrients in the studied weakly developed soils were high as compared with literature data on deeply developed forest soils. Under conditions of rapid water flow through the strongly structured mineral soil at the beech site, almost no retention of DOM took place and thus the influence of the distribution of organically bound nutrients between the DOM fractions on the export of DON, DOP, and DOS was negligible.     

Metals in Sediments of the Upper Laguna Madre

The Laguna Madre system is the largest hypersaline coastal basin in the United States. Surface sediments from 22 Upper Laguna Madre (ULM) sites were analyzed for grain size and metals (Cd, Cu, Ba, Cr, Mn, Ni, Pb, V, Zn, Fe, and Al) to assess the extent of contamination in the area. Sediments were found to consist mainly of sand texture. Clay and silts were minor constituents (<10%) of the sediments. Anomalies in metal concentrations were found at some sites and were related to probable sources, i.e., recreational and industrial activities. Concentrations of metals were normalized to grain size, Al, and Fe to distinguish natural and anthropogenic sources. Most metals showed positive correlations (p < 0.001) with Fe and Al, suggesting a natural variability of metal concentrations in sediments. Concentrations of metals, except Cd and Pb, at most sites were found to be below threshold concentrations thought to produce toxic effects in marine and estuarine organisms.     

Seasonal distribution of trace metals in suspended particulate and bottom sediments of four microtidal river estuaries,west coast of India

ABSTRACT

The seasonal distribution of metals (V, Cr, Co, Cu, Ni, Zn, Pb, Mn, Fe, Al and Ti) in suspended and bottom sediments of four minor estuaries (Terekhol, Chapora, Sal and Talpona rivers) of Goa, India was investigated to understand the metal distribution process in the estuarine region. The highest particulate-metal concentrations were found in low-salinity regions of all the estuaries, in the wet season (e.g. in the Terekhol River, the averages in ppm were Co: 53, Ni: 197, Cu: 208, Zn: 212 and Pb: 65) compared to the dry season averages (Co: 27, Ni: 76, Cu: 105, Zn: 164 and Pb: 13 ppm). The estuarine-mixing diagrams showed non-conservative behaviour in both seasons. The Sal River had the highest particulate-metal concentration (Co: 106, Ni: 300 and Zn: 323 ppm), suggesting an anthropogenic input. The enrichment factor for suspended matter was higher than bottom sediments with extremely high enrichment for Mn (>10). The Geo-accumulation index displayed unpolluted to polluted class for all metals. The study highlights the important role played by small estuaries in seasonal metal release and accumulation along the coastal region.     

Coupling of a Column System with ICP‐MS for the Characterisation of Colloid‐mediated Metal(loid) Transport in Porous Media

In this work a coupling method for the characterisation of colloid‐mediated transport of the metal(loid) species in porous media was developed. For this transport experiments quartz sand was used as column packing material and the synthetic three‐layer clay mineral laponite as model colloid. The determination of colloids was conducted by means of UV detection. The quantification of the metal(loid) ions was carried out in two different ways: (1) The fractions collected at the column outlet were analysed with an inductively coupled plasma mass spectrometer (ICP‐MS) (offline measurements); (2) the column system was directly coupled with ICP‐MS (online measurements). In the column experiments the influence of laponite colloids on the transport of Cu, Pb, Zn, Pt and As species was investigated. In the offline experiments as a consequence of dilution during sample preparation no metal(loid) species at the column outlet could be found. Unlike this the breakthrough of all metal(loid)s could be detected under the same experimental column conditions in the coupling experiments. This coupling technique offers the online detection of the metal species and colloidal particles with high resolution even at low concentrations and without any time‐consuming preparation. The coupling experiments have shown that the laponite particles accelerate the transport of the cationic metals. For anionic metal(loid) species no influence of laponite on their transport behaviour was found.     

泥炭沼泽不同植物群落中地表糙度变化及其影响机制

对藏南沉错CCl孔216个沉积物样品进行了15种金属元素含量的测试,研究金属元素含量的分布特征,以及与粒度参数的变化关系．结果显示：金属元素的分布特征可分为三组,K、Na、Mg、Al、Ti、Ba、Cu、Zn、Fe、Pb、Cr、V等12种元素具有较为相似的变化趋势;Ca和Sr变化趋势相同;而Mn与其他任何一种元素都不相似．元素分布与粒度参数的相关分析结果表明,Ca、Ti、Pb的变化与沉积物粒度没有明显的关系;K、Na、Al、Ba、Cu、Fe、Cr、V等8种元素与沉积物粘土含量（〈4um）呈正相关关系;Mg、Zn、Mn与粉砂含量（4—63μm）呈正相关关系;而Sr与砂含量（〉63gm）呈正相关关系本研究中大部分元素的粒度效应与其他湖泊、海洋等水体沉积物中元素的粒度效应具有一致的结果．与本岩芯已有的过去1400年来的环境重建资料对比可以发现,在不同的环境变化阶段,元素组合特征都与湖区环境状况具有较好的对应性．其中大部分元素的含量变化受物源条件即流域风化侵蚀程度的影响,而Ca含量不受沉积物粒度变化影响,且与沉积物中碳酸盐含量、Sr／Ba具有很好的相关性,说明其变化受物源条件影响小,而主要与湖水理化性质、蒸发强度以及湖泊沉积过程有关．     

Trace metal concentrations in southern right whale (Eubalaena australis) at Península Valdés, Argentina

The presence of essential (Fe, Mn, Zn, Cu, Ni and Al) and non-essential trace metals (Cd and Pb) was tested in liver (N=26) and kidney (N=42) from dead Southern Right Whale (SRW--Eubalaena australis) calves found beached in Península Valdés, Argentina. Essential metals were detected in all samples, particularly in hepatic tissue; though Ni and Al were accumulated mainly in the kidney. Cd and Pb were not detected in any samples. Sex and length of calves did not influence metal levels found, nor did the geographic location of carcasses. Our findings for essential metals were similar to those reported for mysticetes in other parts of the world. Except for a previous report on one SRW calf, this is the first data on trace metals for this species in Patagonia. This information is vital for SRW management considering increasing human pressures impacting their feeding and breeding grounds.