Chemical speciation of inorganic pollutants in river–estuary–sea water systems

Monitoring studies and thermodynamic modeling were used to reveal the changes of inorganic chemical species of some water pollutants (nutrients and trace metals such as Fe, Mn, Zn, Cu, Cd and Pb) inthe river-estuary-sea water system. The case studies were two rivers, Kamchiya and Ropotamo, representing part of the Bulgarian Black Sea water catchment area, and having different flow characteristics. There were no major differences in inorganic chemical species of the two river systems. NO3(-) and NO2(-) chemical species showed no changes along the river-estuary-sea water system. Concerning phosphates six different species were calculated and differences between the three parts of the systems were established. The HPO4(2-) and H2PO4(-) species were found to be dominant in river waters. The H2PO4(-) species quickly decreased at the expense of HPO4(2-) and Ca, Mg and Na phosphate complexes in estuary and seawater. Trace metals showed a great variety of chemical species. Fe(OH)2(+) species prevailed in river waters, and Fe(OH)3(0) species--in sea waters. Me2+ and MeCO3(0) (Me = Cu, Pb) and PbHCO3(+) were dominant in river waters, while Cu(CO3)2(2-) and PbCl(-) species appear also in sea waters. Cd2+ species prevailed in river and estuary waters, and CdCln(2-n) (n = 1-3) species, in seawater. Free Zn2+ species predominated in all systems but downstream their percentage decreased at the expense of Zn phosphates, carbonates,sulfates and chlorides complexes. Only free Mn2+ species were dominant along the systems.     

Determination of heavy metals and metals levels in five fish species from I??kl? Dam Lake and Karaca?ren Dam Lake (Turkey)

The concentrations of heavy metals and metals (Zn, Pb, Bi, Cd, Ni, Co, Fe, Mn, Mg, Cu, Cr, Ca, Sr, Na, Li, K) were measured in muscle of five species Cyprinus carpio (from I??kl? dam), Scardinius erythrophthalmus (from I??kl? dam), Tinca tinca (from I??kl? dam), C. carpio (from Karaca?ren dam), Carassius carassius (from Karaca?ren dam) caught from I??kl? and Karaca?ren. The highest metal was Na (466.95 μg/g) in C. carassius, while the lowest levels were Fe (0.37 μg/g) and Cu (0.37 μg/g) in C. carpio from I??kl? dam. The mean concentrations μg/g d.w. some of heavy metals in muscle of C. carpio (from I??kl? dam), S. erythrophthalmus (from I??kl? dam), T. tinca (from I??kl? dam), C. carpio (from Karaca?ren dam), C. carassius (from Karaca?ren dam) were as follows: Cd 2.00-2.10-1.95-2.06-2.27, Zn 4.36-2.64-13.13-13.33-24.47, Pb 1.65-1.24-1.90-2.37-2.41, Co 2.46-2.37-2.48-2.58-2.80, Mg 138.51-154.35-218.59-204.58-202.16, Fe 0.37-2.62-3.17-3.01-12.33, respectively.     

Concentration of trace elements in feathers of waterfowl,Korea

Cadmium (Cd), lead (Pb), chromium (Cr), copper (Cu), manganese (Mn), zinc (Zn), and iron (Fe) were analyzed in the breast feather of white-fronted geese (Anser albifrons, n?=?15), mallards (Anas platyrhynchos, n?=?4), and spot-billed ducks (Anas poecilorhyncha, n?=?13) found dead in Gimpo, Korea. All of the mallards and eight of the 13 spot-billed ducks had embedded shot. Concentrations of Pb, Cr, Cu, Mn, Zn, and Fe were significantly different among waterfowl species. Mallards with embedded shot had relatively higher Pb, Cr, Mn, and Fe concentrations than the other species. Cd and Cr in feathers of waterfowl species were within the range reported for other birds, and no specimen exceeded the tentative threshold effect levels of Cd (2 μg/g dry weight (dw)) and Cr (2.8 μg/g dw) for birds. However, Pb in feathers of all four mallards and two spot-billed ducks exceeded the threshold for deleterious effects (>4 μg/g dw). Essential elements such as Cu, Mn, Zn, and Fe in the feather of waterfowl species were not at toxic levels and within the background or normal range for the homeostatic mechanisms.     

Accumulation of some heavy metals in Hysterothylacium aduncum (Nematoda) and its host sea bream, Sparus aurata (Sparidae) from North-Eastern Mediterranean Sea (Iskenderun Bay)

The sea bream??s nematode and Sparus aurata, sampled from the Iskenderun Bay, Mediterranean, in March 2008 were analyzed by inductively coupled plasma?Catomic emission spectrometry for their some heavy metal (Cd, Cr, Cu, Fe, Hg, Mn, Mg, Pb, and Zn) levels. The metal concentrations of the parasites were compared to different organs (liver, muscle, gill, intestine, and skin) of the fish hosts. There were significant differences in Cd, Cr, Cu, Fe, Mn, Zn, Hg, Mg, and Pb concentrations in tissues of fish and its parasite. The parasite Cd, Cu, and Pb concentration was higher than the other tissues. Furthermore, significant differences were detected in the heavy metal accumulations between the parasitized and unparasitized fish tissues in Cd, Cu, Hg, and Pb concentrations. The Cd, Hg, and Pb concentrations were found in fish muscle at mean concentrations over the permissible limits proposed by the Food and Agriculture Organization.     

Heavy Metal Levels in Biota and Sediments in the Northern Coast of the Marmara Sea

Concentration of Cd, Co, Cr, Ni, Zn, Fe, Mn, Pb and Cu were determinedin biota and sediment samples collected from the Marmara Sea in Turkey. The levels of Zn, Fe, Mn, Pb and Cu in the macroalgae are higher than previous studies in the Marmara Sea. Moreover, Cu and Zn concentrations at the present study are significantly high than Bosphorus and Black Sea algae. The order heavy metal concentrations in the mussel samples was: Fe > Zn > Ni > Mn > Cu > Pb > Cr > Cd > Co. The metal concentrations are generally lower when compared with the Black Sea mussels except Pb. At the same time, concentrations of Pb, Cu and Zn in the mussel species are lower when compared with the results in the Aegean Sea. The ranges of Mn and Cu in the tested fish samples are higher than Black Sea fish. On the other hand, Cd, Co, Cr, Zn and Pb concentrations are lower. The northern coast of the Marmara Sea having the highest metal concentrations in sediments as follows: Co, Cr, Ni, Fe at ?arköy ; Pb, Cu at M. Ere?li; Cd, Zn, Mn at Menek?e. The heavy metal levels in the sediment samples are lower than other areas in the Marmara Sea.     

Associations of cadmium, zinc, and lead in soils from a lead and zinc mining area as studied by single and sequential extractions

An exploratory study of the area surrounding a historical Pb?CZn mining and smelting area in Zawar, India, detected significant contamination of the terrestrial environment by heavy metals. Soils (n?=?87) were analyzed for pH, EC, total organic matter (TOM), Pb, Zn, Mn, and Cd levels. The statistical analysis indicated that the frequency distribution of the analyzed parameters for these soils was not normal. The median concentrations of metals in surface soils were: Pb 420.21 ?? g/g, Zn 870.25 ?? g/g, Mn 696.70 ?? g/g, and Cd 2.09 ?? g/g. Zn concentrations were significantly correlated with Cd (r?=?0.867), indicating that levels of Cd are dependent on Zn. However, pH, electrical conductivity and total organic matter were not correlated significantly with Cd, Pb, Zn, and Mn. To assess the potential mobility of Cd, Pb, and Zn in soils, single (EDTA) as well as sequential extraction scheme (modified BCR) were applied to representative (n?=?23) soil samples. The amount of Cd, Pb, and Zn extracted by EDTA and their total concentrations showed linear positive correlation, which are statistically significant (r values for Cd, Pb, and Zn being 0.901, 0.971, and 0.795, respectively, and P values being <0.001). The correlation coefficients indicate a strong relation between EDTA-extractable metal and total metal. These results appear to justify the use of ??total?? metal contents as a useful preliminary indicator of areas where the risks of metal excess or deficiency are high. The EDTA extractability was maximum for Cd followed by Pb and Zn in soils from all the locations. As indicated by single extraction, the apparent mobility and potential bioavailability of metals in soils followed the order: Cd ?? Pb >?> Zn. Soil samples were sequentially extracted (modified BCR) so that solid pools of Cd, Zn, and Pb could be partitioned into four operationally defined fractions viz. acid-soluble, reducible, oxidizable, and residual. Cadmium was present appreciably (39.41%) in the acid-soluble fraction and zinc was predominantly associated (32.42%) with residual fraction. Pb (66.86%) and Zn (30.44%) were present mainly in the reducible fraction. Assuming that the mobility and bioavailability are related to solubility of geochemical forms of metals and decrease in the order of extraction, the apparent mobility and potential metal bioavailability for these contaminated soil samples is Cd > Zn > Pb.     

Total concentrations, fractionation and mobility of heavy metals in soils of urban area of Guwahati, India

This work describes the results of assessment of the heavy metals, Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn in urban soil of Guwahati City, India from 31 sites of five different land use types covering residential, commercial, industrial, public utilities, and roadside. Sequential extraction procedure was used to evaluate the relative distribution of the eight metals in exchangeable, carbonate, reducible (Fe?CMn oxide), organic and sulfide, and residual fractions. Of the eight metals, Cd and Co occur in lower concentrations (Cd <?< Co) in all types of land, and concentration variation from one type of land use to another is not much significant for both the metals. Ni presence is more than Co, and the concentrations show some variation depending on land use status. Average Cr and Cu concentrations are ??100?mg/kg, but Cr has a significantly higher presence in industrial land use. The results are similar in case of Pb. The two metals, Mn and Zn have domination over the other metals, and the values are ??300?mg/kg. Industrial and roadside soil contains much more Mn, while commercial soil is most enriched with Zn. Of the metals, Ni has the largest proportion (~42%) bound to the exchangeable fraction and Co, Cr, and Pb also have appreciable proportion bound to the same fraction. A significant amount of Co is associated with carbonates. The reducible fraction has bound considerable quantity of Mn and Zn, while most of Cu is associated with the organic and sulfide fraction. Both Cd and Pb are dominantly associated with the residual fraction. Computation of the mobility factor of the metals indicates Mn to be the most mobile metal present in the soil samples.     

Biomonitoring study of heavy metals in biota and sediments in the South Eastern coast of Mediterranean sea, Egypt

Concentrations of Cd, Cu, Co, Zn, Mn and Fe were determined in biota and sediment samples collected from the Eastern Harbour and El-Mex Bay in the Mediterranean Sea, Egypt. The levels of Cu, Co, Zn, Mn and Fe in the macroalgae, Ulva lactuca, Enteromorpha compressa (green algae) and Jania rubens (red algae), recorded high concentrations except for Cd. Moreover, Fe was the most predominant metal in the seaweed. The two species of bivalves, Donax trunculus and Paphia textile, showed different amounts of metals in their tissue. The abundance of heavy metal concentrations in the mussel samples was found in the order Fe> Zn> Mn> Cu> Co> Cd and Fe> Zn> Mn> Cu> Cd> Co, respectively for the two species. The metals concentrations were generally higher compared with the previous studies in mussels from the same area. The levels of metals accumulated in the investigated fish samples, Saurida undosquamis, Siganus rivulatus, Lithognathus mormyrus and Sphyraena sphyraena, were higher than those of Marmara Sea (Turkey), for Co and Cd and lower for Cu, Zn, Mn and Fe. El-Mex Bay having the highest metals concentration in sediments as their order of abundance were Fe> Zn> Mn> Cu> Cd> Co. Nevertheless, a high variability in the metal levels occurs among the studied algae and biota and also between the investigated Harbour. A significant correlations (p < 0.05) were found for each of Zn and Fe in P. textile and of Co in D. trunculus relative to their concentrations in surficial sediments.     

Speciation of metals in bed sediments and water of Qaraaoun Reservoir, Lebanon

Determination of only total element in sediments does not give an accurate estimate of the likely environmental impacts. Speciation study of metals in sediment provides information on the potential availability of metals (toxic) to biota under various environmental conditions. In water, the toxic metal specie is the free hydrated metal ion. The toxicity of metals depends especially on their chemical forms rather than their total metal content. The present study focuses on Qaraaoun Reservoir, Lebanon. Earlier studies focused only on total metal concentrations in sediment and water. The objective of this study was to determine metal speciation (Fe, Cr, Ni, Zn, Cu, Pb, Cd) in the (operationally defined) sediment chemical fractions and metal speciation in reservoir water. This would reflect on metal bioavailability and toxicity. Water samples and bed sediments were collected from nine sites during the dry season and a sequential chemical fraction scheme was applied to the <75-??m sieve sediment fraction. Metal content in each fraction was determined by the FAAS technique. The data showed that the highest percentages of total metal content in sediment fractions were for: Fe in residual followed by reducible, Cr and Ni in residual and in reducible, Cu in organic followed by exchangeable, Zn in residual and in organic, Pb in organic and carbonate, Cd was mainly in carbonate. Total metal content in water was determined by ICP-MS technique and aqueous metal speciation was predicted using AQUACHEM software interfaced to PHREEQC geochemical computer model. The water speciation data predicted that a high percentage of Pb and Ni were present as carbonate complex species and low percentages as free hydrated ions, highest percentage of Zn as carbonate complex species followed by free hydrated ion, highest percentage of Cd as free hydrated ion followed by carbonate complex species. The sensitivity attempt of free hydrated ion of Ni, Zn, Pb, and Cd in reservoir water revealed dependence of Zn and Cd on pH and alkalinity, while Ni and Pb were only dependent on pH.     

Source discrimination of heavy metals in sediment and water of To Lich River in Hanoi City using multivariate statistical approaches

The concentrations of Mn, Fe, Ni, Cr, Cu, Pb, Zn, As, and Cd were determined to evaluate the level of contamination of To Lich River in Hanoi City. All metal concentrations in 0–10-cm water samples, except Mn, were lower than the maximum permitted concentration for irrigation water standard. Meanwhile, concentrations of As, Cd, and Zn in 0–30-cm sediments were likely to have adverse effects on agriculture and aquatic life. Sediment pollution assessment was undertaken using enrichment factor and geoaccumulation index (I _geo). The I _geo results indicated that the sediment was not polluted with Cr, Mn, Fe, and Ni, and the pollution level increased in the order of Cu < Pb < Zn < As < Cd. Meanwhile, significant enrichment was shown for Cd, As, Zn, and Pb. Cluster and principal component analyses suggest that As and Mn in sediment were derived from both lithogenic and anthropogenic sources, while Cu, Pb, Zn, Cr, Cd, and Ni originated from anthropogenic sources such as vehicular fumes for Pb and metallic discharge from industrial sources and fertilizer application for other metals.     

Welding fumes from stainless steel gas metal arc processes contain multiple manganese chemical species

Fumes from a group of gas metal arc welding (GMAW) processes used on stainless steel were generated using three different metal transfer modes and four different shield gases. The objective was to identify and measure manganese (Mn) species in the fumes, and identify processes that are minimal generators of Mn species. The robotic welding system was operated in short-circuit (SC) mode (Ar/CO2 and He/Ar), axial spray (AXS) mode (Ar/O2 and Ar/CO2), and pulsed axial-spray (PAXS) mode (Ar/O2). The fumes were analyzed for Mn by a sequential extraction process followed by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) analysis, and by X-ray diffraction (XRD). Total elemental Mn, iron (Fe), chromium (Cr) and nickel (Ni) were separately measured after aqua regia digestion and ICP-AES analysis. Soluble Mn2+, Fe2+, Fe3+, and Ni2+ in a simple biological buffer (phosphate-buffered saline) were determined at pH 7.2 and 5.0 after 2 h incubation at 37 C by ion chromatography. Results indicate that Mn was present in soluble form, acid-soluble form, and acid-soluble form after reduction by hydroxylamine, which represents soluble Mn0 and Mn2+ compounds, other Mn2+ compounds, and (Mn3+ and Mn4+) compounds, respectively. The dominant fraction was the acid-soluble Mn2+ fraction, but results varied with the process and shield gas. Soluble Mn mass percent in the fume ranged from 0.2 to 0.9%, acid-soluble Mn2+ compounds ranged from 2.6 to 9.3%, and acid plus reducing agent-soluble (Mn3+ and Mn4+) compounds ranged from 0.6 to 5.1%. Total Mn composition ranged from 7 to 15%. XRD results showed fumes had a crystalline content of 90-99% Fe3O4, and showed evidence of multiple Mn oxides, but overlaps and weak signals limited identification. Small amounts of the Mn2+ in the fume (<0.01 to ≈ 1% or <0.1 to ≈ 10 microg ml(-1)) and Ni2+ (<0.01 to ≈ 0.2% or <0.1 to ≈ 2 mg ml(-1)) ions were found in biological buffer media, but amounts were highly dependent on pH and the welding process. Mn generation rates for the fractions were tabulated, and the influence of ozone is discussed. The conclusions are that exposures to welding fumes include multiple Mn species, both soluble and insoluble, and that exposures to Mn species vary with specific processes and shield gases.     

The comparison of heavy metal accumulation ratios of some fish species in Enne Dame Lake (Kütahya/Turkey)

The metal accumulation levels for muscle, skin, gill, liver and intestine tissues of some Cyprinidae species (Carassius carassius, Condrostoma nasus, Leuciscus cephalus and Alburnus alburnus) in Enne Dame Lake (Kütahya/Turkey), which is mostly fed by hot spring waters, were investigated. Analyses were performed for copper (Cu), zinc (Zn), manganese (Mn), iron (Fe), cobalt (Co), magnesium (Mg), nickel (Ni), chrome (Cr) and boron (B) using inductively coupled plasma-optic emission spectroscopy (ICP-OES), and cadmium (Cd) using atomic absorption spectrophotometer (AAS) utilizing microwave digestion techniques. The concentrations of the heavy metals found in the fish varied in the follow ing ranges: Cu: < DL-7.04, Zn: 6.96-357.25, Mn: < DL-20.70, Ni: < DL-6.21, Fe: 9.62-2500.33, Cr: < DL-1.74, Co: < DL-0.54, Cd: 0.01-0.27 and Mg: 197.44-904.90 mg/kg wet weight. While B had the second highest concentration in the water of the lake, it was not encountered in any tissue of the investigated species. In all tissues and the species, While the bioaccumulation factors (BAFs) of Mn, Zn, Fe and Cu were remarkably high, the BAFs of Mg, Cr, Co, and B were also fairly low or none. Although the heavy metal accumulation levels for the muscle were generally lower than other tissues, there were some exceptions. Cd level in the muscle of C. carassius was higher than the permissible limit stated by Turkish legislation, FAO and WHO. The mean metal amounts for all the investigated tissues and species are statistically compared and discussed in this study.     

Application of sequential leaching, risk indices and multivariate statistics to evaluate heavy metal contamination of estuarine sediments: Dhamara Estuary, East Coast of India

In the present study, concentration of some selected trace metals (Fe, Mn, Ni, Co, Pb, Zn, Cu, Cr and Cd) are measured in Brahmani, Baitarani river complex along with Dhamara estuary and its near shore. Chemical partitioning has been made to establish association of metals into different geochemical phases. The exchangeable fraction is having high environmental risk among non-lithogeneous phases due to greater potential for mobility into pore water. The metals with highest bio-availability being Cd, Zn and Cr. The metals like Mn, Zn, Cd and Cu represent an appreciable portion in carbonate phase. Fe–Mn oxides act as efficient scavenger for most of the metals playing a prime role in controlling their fate and transport. Among non-lithogeneous phases apart from reducible, Cr showed a significant enrichment in organic phase. Risk assessment code values indicate that all metals except Fe fall under medium-risk zone. In estuarine zone Cd, Zn, Pb and Cr are released to 32.43, 26.10, 21.81 and 20 %, respectively, indicating their significant bio-availability pose high ecological risk. A quantitative approach has been made through the use of different risk indices like enrichment factor, geo-accumulation index and pollution load index. Factor analysis indicates that in riverine zone, Fe–Mn oxides/hydroxides seem to play an important role in scavenging metals, in estuarine zone, organic precipitation and adsorption to the fine silt and clay particles while in coastal zone, co-precipitation with Fe could be the mechanism for the same. Canonical discriminant function indicates that it is highly successful in discriminating the groups as predicted.     

Study of leachability and fractional alteration of arsenic and co-existing elements in stabilized contaminated sludge using a flow-through extraction system

This study investigates the stabilization of As in the contaminated sludge after treatment with MnO(2) or Ca(OH)(2), and the influence of the stabilizing materials on the leachability of the co-existing elements Pb and Zn. By exploiting a continuous-flow assembly facilitating a modified Wenzel's sequential extraction scheme (designed for the fractionation of arsenic), it is possible to ascertain the leachability, mobility and fractional alteration of these elements under stimulated natural (flow-through) leaching conditions. The fractionation data show that more than 80% of As, Pb and Zn in the untreated sludge are bound in the amorphous Fe oxides fraction and residual fraction. The addition of MnO(2) has only an insignificant effect on As fractional transformation, while Ca(OH)(2) caused an increase in As mobility. For Pb, the decrease in leachability was clearly visible. The extractable Pb was reduced by 18% and 40% in stabilized MnO(2) and Ca(OH)(2) sludge samples, respectively. Unlike that of Pb, the mobility of Zn was not affected by the additives used. Their fractional distribution patterns before and after the stabilization process remained the same. The ability to produce detailed leaching profiles for As and other elements (Pb, Zn, Ca, Mn and Fe) meant that elemental associations in individual fractions could be examined. From the MnO(2)-treated sludge, the coincidence of the As, Pb, Zn, Fe, and Mn peaks seems to indicate a close association of these elements in the Fe-oxides-bound fraction. Furthermore, the leaching profiles may be used as evidence of a strong affinity between these elements and added MnO(2).     

Chemometric study on the trace metal accumulation in the sediments of the Cochin Estuary―Southwest coast of India

The distribution and accumulation of trace metals in the sediments of the Cochin estuary during the pre-monsoon, monsoon and post-monsoon periods were investigated. Sediment samples from 14 locations were collected and analysed for the metal contents (Mg, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb), organic carbon, total nitrogen, total sulphur and grain size. The data were processed using statistical tools like correlation, factor and cluster analysis. The study revealed an enrichment of Cd and Zn in the study area particularly at station 2, which is confirmed by enrichment factor, contamination factor and geoaccumulation index. The factor analysis revealed that the source of Cd and Zn may be same. The study indicated that the spatial variation for the metals like Mg, Cr, Fe, Co, Ni, Cu, Zn, Cd and Pb were predominant unlike Mn which shows a temporal variation. The strong association of trace metals with Fe and Mn hydroxides and oxides are prominent along the Cochin estuary. The anthropogenic inputs of industrial effluents mainly control the trace metals enrichment in the Cochin estuary.     

Heavy Metals Monitoring using Bivalves from Mediterranean Sea and Red Sea

The concentrations of heavy metals (Cd, Co, Cu, Fe, Mn, Ni, Pd and Zn) were measured in the Bivalves (Modiolus auriculatus and Donax trunculus) collected from the Egyptian coasts of Mediterranean Sea and Brachiodonates sp. from the Egyptian coasts of Red Sea. The average concentrations of the heavy metals analyzed exhibited the following decreasing order: Fe > Zn > Cu > Mn > Ni > Co > Pb > Cd for both Mediterranean Sea and Red Sea. The analyses of Cd, Co, Ni, Pb, and Zn showed higher average concentrations for samples collected from Red Sea than that collected from Mediterranean Sea, while Fe, Cu and Mn showed the reverse results. Fe was used as a normalizing agent for all studied metals and exhibited presence of two locations from each of Mediterranean Sea and Red Sea have anthropogenic inputs of heavy metals. These results suggest that the coastal area in both Mediterranean Sea and Red Sea of Egypt might be considered relatively unpolluted with heavy metal.     

Chemical fractionation of heavy metals in urban soils of Guangzhou, China

Knowledge of the total concentration of heavy metals is not enough to fully assess the environmental impact of urban soils. For this reason, the determination of metal speciation is important to evaluate their environment and the mobilization capacity. Sequential extraction technique proposed by the former European Community Bureau of Reference (BCR) was used to speciate Cd, Cu, Fe, Mn, Ni, Pb, and Zn in urban soils from Guangzhou into four operationally defined fractions: HOAc extractable, reducible, oxidizable, and residual. The Cu, Fe, Ni, and Zn were predominately located in the residual fraction, Pb in the reducible fraction, and Cd and Mn within the HOAc extractable fraction. The order of Cd in each fraction was generally HOAc extractable > reducible > residual > oxidizable; Cu and Fe were residual > reducible > oxidizable > HOAc extractable; Mn was HOAc extractable > residual > reducible > oxidizable; Ni and Zn were residual > reducible > HOAc extractable > oxidizable; and Pb was reducible > residual > oxidizable > HOAc extractable. Cadmium was identified as being the most mobile of the elements, followed by Mn, Zn, Ni, Cu, Pb and Fe. Iron–Mn oxides can play an important role in binding Cd, Cu, Ni, Pb, and Zn and in decreasing their proportion associated with the residual fraction in the soils. With total concentrations of Cd, Cu, Ni, Pb, Zn, and Mn increase, these metals more easily release and may produce more negative effects on the urban environment.     

Monitoring of trace elements in honey from the Republic of Macedonia by atomic absorption spectrometry

Contents of Zn, Cu, Fe, Mn, Cd, Na, K, Ca and Mg in 123 honey samples from different regions of the Republic of Macedonia were determined by atomic absorption spectrometry. A microwave digestion system was applied for digestion of the samples. The mean content for the elements determined was found to be: 2.252, 0.696, 1.885, 1.752, 0.004, 29.52, 984.8, 40.11, 18.24 mg kg(-1) for Zn, Cu, Fe, Mn, Cd, Na, K, Ca and Mg, respectively. Based on a comparison of statistical parameters, the spatial distribution of particular elements in Macedonian honey and the results of factor analysis, two natural and one anthropogenic geochemical associations were identified. The natural geochemical associations (Mg, Mn, Ca, K and Fe, Zn, Ca, -K, -Na) are influenced mainly by lithology. The anthropogenic associations (Cd and -Cu) are mostly a result of metallurgical activities, namely lead production in the town of Veles.     

Determination of metal-humic complexes, free metal ions and total concentrations in natural waters

A comparison of two systems for the quantitation of metal-humic complexes and free metal ions, consisting of the separation by coupled ion exchange columns followed by detection by inductively coupled plasma mass spectrometry or cold vapour atomic fluorescence spectrometry, is presented. The systems evaluated comprised the serially coupled anion and cation exchangers, Sephadex A-25/Chelex 100 and Dowex 1X8/Chelamine Metalfix. Separation and preconcentration of the species studied were accomplished with both systems, elution being carried out using 2 M HNO3. Total concentrations, metal-humic complex fractions and free metal ion fractions of Al, Ba, Cd, Co, Cu, Fe, Hg, Mn, Pb, Sr, U and Zn in nine natural waters were determined. Statistical evaluation of the data from the two cation exchange materials, including results for additional elements, showed better precision (for Al, Ba, Cr, Cu and Mo) and higher recoveries (Al, Ba, Cd, Fe, Sr and Zn) for Chelex 100 than Chelamine Metalfix for free metal ions. On the other hand, Chelamine Metalfix recovered a significantly greater amount of Ni. The amounts of metal-humic complexes were compared with modelled distributions of these species, and one advantage of the preferred Sephadex A-25/Chelex 100 system is that the elements studied are all correctly classified with respect to their binding strengths to humic substances, which is not the case with the Dowex 1X8/Chelamine Metalfix pair. With the preferred system, metal-humic complexes can be reliably determined, as indicated by the results of equilibrium speciation modelling. However, comparison with the total concentrations showed statistically significant, non-quantitative recoveries of Al, Cu, Hg, Mn, U and Zn from some samples. Thus a combination of speciation and total concentration measurements is required to obtain a complete representation of the distribution of trace elements in natural waters.     

Assessment of the Quality Characteristics of Two Lakes (Koronia and Volvi) of N. Greece

Quality parameters from 17 sampling stations from Lake Koronia and 18 from Lake Volvi were determined during sampling period of one year. Physicochemical parameters (pH, conductivity, DO) did not show remarkable differences neither between sampling sites nor between sampling periods. Nutrient concentrations (nitrogen and phosphorus compounds) were higher in lake Koronia than in Volvi showing relatively small temporal and spatial variations. As far as heavy metals in sediments, lake Koronia is considerably more polluted than Volvi lake especially with the metals Fe, Mn, Zn, Pb and Cd. The mean total concentrations of metals in lake Koronia decrease in the order Mn > Zn > Cr > Pb > Cu > Fe > Cd. The mean total concentrations of metals in lake Volvi decrease in the order Mn > Zn > Cr > Cu > Pb > Fe $>$ Cd.