Mass balance and distribution of sludge-borne trace elements in a silt loam soil following long-term applications of sewage sludge

Soil samples were collected at 15-cm increments to a depth of 75 cm from plots on a silt loam soil where until several years earlier and for 14 years, anaerobically digested sewage sludge had been annually applied by furrow irrigation. The study protocol consisted of four replications of 6.1 x 12.2-m plots with 0 (T0), 1/4-maximum (T1), 1/2-maximum (T2) and maximum (T3) sludge application rates randomized within blocks. When sludge applications were terminated, maximum sludge-treated plots had received 765 Mg ha-1 (dry weight equivalent) of sludge solids. Total soil concentrations of Cd, Cr, Cu, Ni, Pb and Zn had been significantly enhanced by all sludge application rates to a soil depth of 30 cm. Below the 30-cm depth, total soil Cd was increased to 75 cm, total Zn to 45 cm (T2 and T3 only), total Cr to 60 cm (T2 and T3 only), but total Cu, Pb, and Ni were not increased at depth. Despite the lack of significant increases in subsoil concentrations for some metals, mass balance calculations showed a relatively high proportion of all the above sludge-borne heavy metals to be unaccounted for in the soil profile for each application rate. Mass balance calculations of losses ranged from a high of 60% for Ni to a low of 36% for Cu and Pb. Similar losses were calculated from metal concentrations measured in soil samples taken at the time the sludge was applied. In soil surface samples (0-15 cm) from maximum sludge-treated plots, percentages of total metal concentration extracted with 4.0 M HNO3 ranged from a low of 31 for Zn to a high of 75 for Cu. Efficiency of metal extraction by HNO3 was inconsistent, depending on the soil horizon and sludge treatment, so that evaluation of HNO3-extractable metals is not a reliable method of estimating total metal retention in the profiles. In soil surface samples from maximum sludge-treated plots, the percentage of total metal contents extracted with DTPA ranged from a low of 0.03 for Cr to a high of 59 for Cd. The DTPA extractable levels of Cu, Ni, and Pb were higher in the subsoils of the sludge-treated soils, indicating that these metals had been redistributed from the surface layer to deeper zones in the profile of sludge-amended soil, despite the absence of elevated total concentrations of these three metals in the deeper subsoil.     

Seasonal and time variability of heavy metal content and of its chemical forms in sewage sludges from different wastewater treatment plants

Sewage sludges obtained from seven wastewater treatment plants from the province of Salamanca, Spain, were periodically sampled to determine seasonal and time variation of their elemental composition over 2000 to 2002. The aim of this paper was to provide additional insight to evaluate the potential environmental impact following soil incorporation of these materials as amendments. Aqua regia extractable metals (pseudo total content) of Cd, Cr, Cu, Ni, Pb and Zn were determined and furthermore, the main chemical forms of metals within the sludge were evaluated using a five-step fractionation procedure. All the studied sludges displayed high fertility properties due to their richness of OC, P and K. Total mean concentrations of Cd, Cr, Cu, Ni, Pb and Zn in the sludges were within the regulation of the Spanish legislation. Using an multifactor analysis of variance, significant differences between Cr, Cu, Ni, Pb and Zn pseudo total contents (p<0.01) of sludges at different sites were found while the Cd content was statistically similar. Also significant differences were found between these pseudo total contents of heavy metals in samples collected along the time after three years (0.001相似文献   

Evaluation of metal concentrations in edible vegetables grown in compost amended soil

Agricultural uses of compost usually have a positive effect on the yield of vegetable crops for human consumption. However, compost that contains heavy metals can transfer these components to soils and plants. To evaluate the contamination levels of metals in soil, compost, and edible vegetables, the Mn, Zn, Pb, Cd, Cu, and Ni total contents were measured. Metal availability in soils, as well as other variables – the pH, CEC (cation exchange capacity), total nitrogen, organic carbon, particle size distribution and mineralogy of the clay fraction – were examined in the soil samples. The analysed compost samples were produced from urban solid waste, cattle manure, and edible vegetable and tree pruning residues. The values of pH, CEC, total nitrogen, organic matter, exchangeable hydrogen and carboxylic groups were measured in the compost samples. Of the six metals examined in the soils, in general, Mn and Zn attained the highest concentrations, followed by Cu. Relatively high Mn, Zn, Cu, Cd and Pb concentrations were found in the soils. Metal concentrations extracted with DTPA were below the critical levels in soils, i.e. the levels above which toxicity is likely. In general, Zn, Pb, Cd, Cu and Ni concentrations in compost were lower than those reported by other workers, while Mn levels were within the range for this metal in compost. The results showed that there was an effect of the vegetable type (p < 0.01) for all the parameters examined. High Pb concentrations were found in lettuce and chive as compared with the tolerance limit for this metal in fresh vegetables in Brazil. Cadmium concentrations were also enhanced in the fresh vegetables compared with the typical concentrations of metals in plants. Zinc, Cu, Cd, and Ni concentrations were lower than the tolerance limits established for foods by the Brazilian legislation.     

Heavy metal behaviour during the activated sludge process I. Extent of soluble and insoluble metal removal

The extent of removal of Ag, Bi, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Tl and Zn and their distribution between the soluble and insoluble phases in the influent, and effluent of the activated sludge process has been studied using a pilot-scale plant operated at sludge ages of 3, 6, 9 and 12 days. Molybdenum, Tl, Co, Mn and Ni were >50% soluble in the influent settled sewage. The mean removals of the former two metals were <3% and the latter three were 35 and 50%. Silver, Bi, Cd, Cr, Cu, Pb and Zn were all <35% soluble in the influent and had substantial removals of >75%. Solubilities were greater in the effluent than the influent with the exception of Mn. The observed overall removals of Ag, Bi, Co, Ni, Pb, Tl and Zn were almost entirely due to insoluble metal removal; Cd, Cr and Cu removals had a significant contribution from soluble metal removal. Overall Mn removal appeared to be solely due to soluble metal removal.     

Application of high Cu compost to Swiss chard and basil

A greenhouse container experiment was conducted to evaluate the effect of high Cu compost on basil and Swiss chard productivity, and the accumulation of As, Ca, Fe, Hg, K, Mg, Na, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, S and Se in growth medium and plant tissue. The Cu content of the compost was over 1200 mg/kg, much higher than Canadian standards for type B compost quality. The treatments consisted of control soil (0% compost), and 20, 40 and 60% (by volume) of high Cu compost added to soil. All compost application treatments (20, 40 and 60%) resulted in increased dry matter yields in Swiss chard and basil. Addition of high Cu compost influenced basil plant development. Plants from the 20 and 40% treatments had higher numbers of buds and flowers. There were no differences between the control and 60% compost treatments with respect to flower initiation. Addition of 20, 40 and 60% compost to the soil resulted in increased EXCH fractions of Cu, but not of Mn and Zn. Compost additions resulted in increase in the HNO(3) extractable, CARB, FeMnOX, and in OM fractions of Cu, Mn and Zn in soils. Compost application increased soil pH and EC, soil HNO(3) extractable Ca, K, Mg, P, Na, B and Pb, but did not alter soil HNO(3) extractable Cd, Co, Cr, Mo, Ni, Se. Increased rates of compost application decreased tissue Ca in basil, tissue Na in both plants, increased tissue K, Mg in both plants, but, did not alter tissue P, Co, Cr, Mo, Ni of either plants, and B in basil. Tissue As, Hg, Pb, and Se from all treatments were under the detection limits of VGA-AAS (for As, Hg, Se) and ICP (for Pb). Compost additions altered basil oil chemical composition. Copper in the essential oil of basil was below 0.25 mg/l. In conclusion, the addition of high rates of relatively immature high Cu compost may not always increase Cu concentration in plants and in plant oils.     

Estuarine capacity in removal of trace metals from contaminated river water, Southern Caspian Sea

In the present investigation, the flocculation of dissolved Cd, Cu, Ni, Pb, Mn and Zn with initial concentrations of 1, 2.5 and 5 mg/L in Tadjan River water during mixing with the Caspian Sea water has been studied in order to determine estuarine capacity to remove dissolved metals in the accidental contamination of the river. The flocculation process was investigated on a series of mixtures with salinities ranging from 0.1 to 11 p.p.t. The flocculation rates were indicative of the nonconservative behaviour of Cd, Cu, Ni, Pb, Mn and Zn during estuarine mixing. The order of the final flocculation rate of dissolved metals at 1, 2.5 and 5 mg/L of initial metal concentrations in the river water is as follows:Cu (99%)>Cd (95%)>Zn (88%)>Mn (85%)>Pb (83%)>Ni (73%), Cu(95.6%)>Pb(92.4%)>Cd (90%)>Zn(88.4%)>Mn (81.6%)>Ni(78.8%) and Cd (100%)>Cu(88%)>Ni (85.2%)>Pb (84%)>Zn (83.2%)>Mn (81.2%), respectively. The results also revealed that removal of dissolved metals is not influenced by pH changes and precipitation processes. The flocculation rates revealed that the overall dissolved metal pollution loads may be reduced to about 70% up to about more than 90% during estuarine mixing of Tadjan River with the Caspian Sea water.     

Trace elements in soils and plants in temperate forest plantations subjected to single and multiple applications of mixed wood ash

Wood ash, a by-product generated in power plants, can be used to fertilize forest plantations to replenish nutrients lost during harvesting. Although wood ash generally contains low levels of trace metals, release of some of these may occur soon after ash application in acid soils. The risk of heavy metal contamination associated with application of mixed wood ash was assessed in six Pinus radiata D. Don plantations, on two types of mineral soil differing in texture, drainage and CECe. Four of the stands received a single application of 4500 kg ha(-1) (March 2003), and in the other two stands the same treatment was applied over three consecutive years (2003-2005). Trace metal (Cd, Cr, Cu, Mn, Ni, Pb, Zn) concentrations were monitored throughout the 3 years in different components of the forest ecosystem--soil solid fraction, soil solution, tree needles, ground vegetation and different mushroom species. Repeated applications of wood ash led to moderate increases in soil extractable Mn and Zn, and Mn in all mushrooms species. However, the maximum concentrations did not reach levels potentially harmful to organisms. Concentrations of Zn, Cu and Cd decreased in some mushroom species, probably because of increased soil pH caused by the treatment. Heavy metal concentrations in tree needles and ground vegetation were not altered. Although the risk of heavy metal contamination appears to be low, the long-term effects of wood ash application must be assessed.     

Quantities and associations of lead, zinc, cadmium, manganese, chromium, nickel, vanadium, and copper in fresh Mississippi delta alluvium and New Orleans alluvial soils

The topic of this study is the effect of anthropogenic metals on the geochemical quality of urban soils. This is accomplished by comparing the metal contents and associations between two alluvial soils of the lower Mississippi River Delta, freshly deposited alluvial parent materials and alluvial soils collected from a nearby urban environment. Fresh alluvium samples (n = 97) were collected from the Bonnet Carré Spillway. The urban alluvial soil samples (n = 4026) were collected from New Orleans and stratified by census tracts (n = 286). The Spillway samples tend to have less Pb and Zn than generally noted for the baseline of natural soils. Except for Mn and V, Spillway alluvium contains significantly less metal than urban soils. For Spillway samples, the median metal content (in microg g(-1)) is 4.7 Pb, 11.1 Zn, 0.7 Cd, 164 Mn, 0.8 Cr, 3.9 Ni, 3.2 V, and 3.9 Cu. For urban soils, the median metal content (in microg g(-1)) is 120 Pb, 130 Zn, 3.2 Cd, 138 Mn, 2.1 Cr, 9.8 Ni, 3.8 V, and 12.7 Cu. Metal associations also differ between Spillway alluvium and urban alluvial soils. Fresh alluvium correlation coefficients between individual metals vary from 0.87 to 0.99 (P < 10(-13)) except for Cr which ranges from 0.57 to 0.68 (P < 10(-7)). The urban soil correlation coefficients for metals and the index value are 0.40-0.98. In urban soils, Pb, Zn, Cr, and Cu are dominant metals and highly associated, with a correlation coefficient ranging from 0.83 to 0.98 (P < 10(-25)). Their strong association justifies the use of GIS to map the integrated soil metal index (sum of the medians of metals by census tract) of New Orleans. Although also positively correlated (0.40-0.68, P < 10(-10)), Cd, Mn, Ni and V differ in their distribution in the city compared to Pb, Zn, Cr and Cu. Overall, significantly higher metal values occur in the inner city and lower values occur in outlying areas. The human health impact of the mixture of metals is not well understood. This study provides empirical data about the mixture and distribution of metals in New Orleans alluvial soils. Given common technical development, especially of traffic flows in cities, similar patterns of soil metals are expected for all US cities and probably international cities as well. Primary prevention of urban metal accumulations is necessary to enhance and sustain the development of urban culture.     

A field survey of metal binding to metallothionein and other cytosolic ligands in liver of eels using an on-line isotope dilution method in combination with size exclusion (SE) high pressure liquid chromatography (HPLC) coupled to Inductively Coupled Plasma time-of-flight Mass Spectrometry (ICP-TOFMS)

The effect of metal exposure on the accumulation and cytosolic speciation of metals in livers of wild populations of European eel with special emphasis on metallothioneins (MT) was studied. Four sampling sites in Flanders showing different degrees of heavy metal contamination were selected for this purpose. An on-line isotope dilution method in combination with size exclusion (SE) high pressure liquid chromatography (HPLC) coupled to Inductively Coupled Plasma time-of-flight Mass Spectrometry (ICP-TOFMS) was used to study the cytosolic speciation of the metals. The distribution of the metals Cd, Cu, Ni, Pb and Zn among cytosolic fractions displayed strong differences. The cytosolic concentration of Cd, Ni and Pb increased proportionally with the total liver levels. However, the cytosolic concentrations of Cu and Zn only increased above a certain liver tissue threshold level. Cd, Cu and Zn, but not Pb and Ni, were largely associated with the MT pool in correspondence with the environmental exposure and liver tissue concentrations. Most of the Pb and Ni and a considerable fraction of Cu and Zn, but not Cd, were associated to High Molecular Weight (HMW) fractions. The relative importance of the Cu and Zn in the HMW fraction decreased with increasing contamination levels while the MT pool became progressively more important. The close relationship between the cytosolic metal load and the total MT levels or the metals bound on the MT pool indicates that the metals, rather than other stress factors, are the major factor determining MT induction.     

腐殖土活性污泥中重金属的浸出行为研究

在不同pH值和腐殖土投加量条件下,对活性污泥中Zn、Ni、Cu和Pb四种重金属的浸出行为进行了研究。结果表明,污泥中Zn和Ni的浸出率随pH值的降低而呈明显升高的趋势,Cu和Pb的浸出率也随pH值的降低而升高,但变化幅度相对较小。在酸性条件下,随着腐殖土投量的增加,活性污泥中Zn、Ni、Cu和Pb的浸出率明显降低;而在中性偏碱性条件下,这种变化趋势不明显。投加腐殖土能明显改变活性污泥中重金属的形态分布,促进重金属的稳定化,进而显著改善重金属的浸出行为。     

Decomposition of belowground litter and metal dynamics in salt marshes (Tagus Estuary, Portugal)

The concentrations of C, Fe, Mn, Zn, Cu, Pb and Cd were determined monthly in decomposing roots of Halimione portulacoides, using litterbag experiments, in two salt marshes of the Tagus estuary with different levels of contamination. Although carbon concentrations varied within a narrow interval during the experiment, litter decomposed rapidly in the first month (weight loss between 0.051 and 0.065 g d(-1)). The time variation of metals was examined in terms of Me/C ratios and metal stocks. Ratios of Fe/C and Mn/C and their metal stocks increased in spring, presumably due to the precipitation of oxides in the surface of decomposing roots. Subsequent decrease of Fe/C and Mn/C ratios suggests the use of Fe and Mn oxides, as electron acceptors, in the organic matter oxidation. Zinc, Cu, Pb and Cd ratios to C were, in general, higher than at initial conditions implying that metal that leached out was slower than carbon. However, metal stocks decreased during the experiment indicating that incorporation or sorption of metals in Fe and Mn oxides did not counterbalance the amount of Zn, Pb and Cd released from decomposing litter. An exception was observed for Cu, since stock in the less contaminated marsh (Pancas) increased during the decomposition, indicating that litter was efficient on Cu binding under more oxidising conditions. These results emphasize the importance of litter decomposition and sediment characteristics on metal cycling in salt marshes.     

兰州某铝厂旧址周围土壤重金属污染及分布特征

研究了兰州某铝厂旧址周围土壤重金属形态特征,找出了该土壤中重金属元素的形态分布及变化规律,分析了引起7种重金属元素形态变化的主要因子。结果表明,该铝厂周围土壤重金属Cu、Mn、Ni、Pb、Zn、Cr、Cd污染严重。各重金属元素的含量随样品采集半径的增加而减少,7种重金属的形态分析结果表明,重金属污染主要以残渣态为主,Cd、Mn和Cr的弱酸态占有较大的比例,其中Cd的生态风险性最高。同时对重金属的环境效应和生态风险作出一定的评价,为治理和改善该地区土壤环境质量积累科学数据。     

Patterns of metal bioaccumulation in two filter-feeding macroinvertebrates: Exposure distribution, inter-species differences and variability across developmental stages

This study focused on the metal bioaccumulation of two aquatic insects (Ephoron virgo and Hydropsyche spp.) in order to evaluate the spatial distribution of metals, the interspecific differences between both filter-feeders and the bioaccumulation dynamics during E. virgo development stages. Hg, Cd, Ni, Cr, As, Pb, Cu, Ti, Zn and Mn were quantified in insects and in suspended particulate matter (SPM) sampled downstream and upstream of a chemical plant, where more than 300,000 t of polluted sediments are deposited. Hg concentrations were one order of magnitude higher downstream of the sediment dump, which showed that the Hg pollution originated in the chemical plant. Cd, Ni, Cr, Pb, Ti, Zn and Mn in invertebrates revealed that metal pollution was present upstream in other parts of the river. Interspecific differences were observed for all metals but Mn; significantly higher concentrations were observed in E. virgo over Hydropsyche exocellata, except for Cd, which showed 10-fold higher values. Hg and Cd increased until E. virgo nymphs reached 11 mm and decreased afterwards in late instars when nymphs were about to emerge. Cr, Pb, Ti and Mn decreased along early instars followed by a steady state in late instars. Similar values were obtained for Cu, As and Zn along all instars. Sexual differences between males and females of E. virgo were observed for Cd, Cu and Mn. Hg and Cd persistence was strong across developmental stages since high concentrations were found in eggs and emerging adults. Because the behavior of different metals varied for the two species and during the developmental stages of E. virgo, care should be taken in the interpretation of insect metal concentrations when analyzing the food chain transfer of metals in river ecosystems.     

Heavy metal pollution of soils affected by the Guadiamar toxic flood

Total heavy metal concentrations were determined in soil samples of seven selected areas along the Guadiamar river valley affected by the toxic flood, after removal of the deposited sludge. Mean total concentrations of nine elements (As, Au, Bi, Cd, Cu, Pb, Sb, Tl and Zn) out of the 23 (As, Au, Ba, Be, Bi, Cd, Co, Cr, Cu, In, Mn, Mo, Ni, Pb, Sb, Sc, Sn, Th, Tl, U, V, Y and Zn) analysed were higher in sludge-covered soils than in unaffected soils. Mean values of total As, Au, Pb, Sb, Tl and Zn in sludge-affected soils were higher than the upper limits for normal soils world-wide. Mean concentrations of Bi, Cd and Cu were within these ranges, although some individual values exceeded the upper limits. In all sampling areas, severe heavy metal pollution was observed in the superficial layers (0-20 cm) of most of the affected soils, which decreased downward in the soil profile. Generally, in soils with more than 25% of clay, concentration of heavy metals below the 20-cm depth decreased to values close to those of the background level of the Guadiamar valley soils, while in coarser soils, heavy metal pollution penetrated below this depth, being noticeable down to a depth of at least 50-80 cm.     

Concentrations of heavy metals and plant nutrients in water, sediments and aquatic macrophytes of anthropogenic lakes (former open cut brown coal mines) differing in stage of acidification.

Concentration of heavy metals (Al, Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, V and Zn) as well as macronutrients (N, P, K, Ca, Mg, S) were measured in water, bottom sediments and plants from anthropogenic lakes in West Poland. The collected plants were: Phragmites australis, Potamogeton natans, Iris pseudoacorus, Juncus effusus, Drepanocladus aduncus, Juncus bulbosus, Phalaris arundinacea, Carex remota and Calamagrostis epigeios. Two reference lakes were sampled for Nymphaea alba, Phragmites australis, Schoenoplectus lacustris, Typha angustifolia and Polygonum hydropiper. These plants contained elevated levels of Cd, Co, Cr, Cu and Mn, and part of the plants contained in addition elevated levels of Mn, Fe, Pb, Ni and Zn. Analyses of water indicated pollution with sulfates, Cd, Co, Ni. Zn, Pb and Cu, and bottom sediments indicated that some of the examined lakes were polluted with Cd, Co and Cr. Strong positive correlations were found between concentrations of Co in water and in plants and between Zn in sediments and plants, indicating the potential of plants for pollution monitoring for this metal. Heavy metal accumulation seemed to be directly associated with the exclusion of Ca and Mg.     

Divalent metal accumulation in freshwater bivalves: an inverse relationship with metal phosphate solubility

Whole soft tissue concentrations of Mn, Co, Ni, Cu, Zn, Pb, Cd and U were measured in two species of freshwater (unionid) bivalves (Hyridella depressa and Velesunio ambiguus) from a minimally polluted site in the Hawkesbury-Nepean River, south-eastern Australia. Although the mean concentrations of metals in the tissue were similar for each bivalve species, their patterns of accumulation were dissimilar. For each metal, positive linear relationships between tissue concentration and shell length (r2 = 0.37-0.77; P < or = 0.001) and tissue dry weight (r2 = 0.29-0.51; P < or = 0.01) were found in H. depressa, but not in V. ambiguus. However, for both species, positive linear relationships were found between the tissue concentration of each divalent metal and Ca tissue concentration (r2 = 0.59-0.97; P < or = 0.001). For both bivalve species, the normalised rates of accumulation of the metals relative to increasing Ca concentration and/or size, were U approximately = Cd > or = Pb > or = Mn > Co > or = Zn > Cu > Ni. The differential rates of accumulation of divalent metals are interpreted as being predominantly governed by their varying loss rates, which are controlled by the differing solubilities (log Ksp values) of the metals in the phosphatic extracellular granules, the demonstrated major sites of metal deposition in the tissue of H. depressa and V. ambiguus. The rates of accumulation of Mn, Co, Zn, Cu and Ni were linearly and inversely related (r2 = 0.91-0.97; P < or = 0.001) to their solubilities as hydrogen phosphates, a finding consistent with the bioaccumulation model previously developed for the alkaline-earth metals. However, for U, Cd and Pb, this linear inverse relationship did not continue to hold, i.e. their rates of accumulation did not increase with decreasing solubility. However, these results are still consistent with the model if U, Cd and Pb are so insoluble in the granules of H. depressa and V. ambiguus over their lifetime (up to approx. 50 years) that there is effectively no loss of these metals, and hence, no differential between their rates of accumulation. The present results reaffirm the use of Ca tissue concentration to predict the tissue concentrations of other divalent metals by explaining up to 94 and 97% of the variability between individual bivalves of H. depressa and V. ambiguus, respectively. The use of Ca tissue concentration to effectively minimise the inherent variability between individuals in their metal tissue improves the ability of an investigator to discern smaller spatial and/or temporal differences in the metal tissue concentrations of these bivalves, and thus to detect metal pollution.     

Aromatic plant production on metal contaminated soils

Field and container experiments were conducted to assess the feasibility of growing aromatic crops in metal contaminated areas and the effect of metals on herbage and oil productivity. The field experiments were conducted in the vicinities of the Non-Ferrous Metals Combine (Zn-Cu smelter) near Plovdiv, Bulgaria using coriander, sage, dill, basil, hyssop, lemon balm, and chamomile grown at various distances from the smelter. Herbage essential oil yields of basil, chamomile, dill, and sage were reduced when they were grown closer to the smelter. Metal removal from the site with the harvestable plant parts was as high as 180 g ha(-1) for Cd, 660 g ha(-1) for Pb, 180 g ha(-1) for Cu, 350 g ha(-1) for Mn, and 205 g ha(-1) for Zn. Sequential extraction of soil demonstrated that metal fractionation was affected by the distance to the smelter. With decreasing distance to the smelter, the transfer factor (TF) for Cu and Zn decreased but increased for Cd, while the bioavailability factor (BF) for Cd, Pb, Cu, Mn, and Zn decreased. Scanning electron microscopy and X-ray microanalyses of contaminated soil verified that most of the Pb, Cd, Mn, Cu, and Zn were in the form of small (<1 microm) particles, although there were larger particles (1-5 microm) with high concentrations of individual metals. This study demonstrated that high concentrations of heavy metals in soil or growth medium did not result in metal transfer into the essential oil. Of the tested metals, only Cu at high concentrations may reduce oil content. Our results demonstrated that aromatic crops may not have significant phytoremediation potential, but growth of these crops in metal contaminated agricultural soils is a feasible alternative. Aromatic crops can provide economic return and metal-free final product, the essential oil.     

Effects of sewage sludge on pH and plant availability of metals in oxidising sulphide mine tailings

A field study was conducted adjacent to the tailings deposit of the Aitik copper mine in the north of Sweden to investigate the effects of sewage sludge on pH and plant availability of Al, Mn, Cu, Zn, Ni, Pb, As, Cr and Cd in the oxidising sulphide tailings. One treatment was supplied with sewage sludge, while the control received NPK-fertiliser. The tailings samples were collected at the beginning and the end of the growing season and extracted by NH(4)NO(3), NH(4)Ac-EDTA and HNO(3). Plant tissue concentrations of the elements were determined in the above-ground parts of barley (Hordeum vulgare) and red fescue (Festuca rubra). The application of sewage sludge resulted in higher crop yields compared to the control, although the buffering capacity and the metal immobilising effect of the sludge were limited. The pH decreased from 6.6 to 4.3 in the control and from 6.4 to 4.8 in the sludge-treated tailings during the growing season, probably due to sulphide oxidation in the tailings. This resulted in increased levels of soluble elements in all treatments studied. Application of sewage sludge resulted in elevated levels of soluble Zn and lower values of soluble As and Cd in the unaltered tailings but increased levels of specifically adsorbed Cu, Ni and As in the oxidised tailings. This was partly reflected in the plants, as the application of sewage sludge resulted in 67 mg Zn kg(-1) in barley grains and 60 mg Zn kg(-1) in red fescue shoots, both values twice as high as the corresponding values in the control, but lower As contents in both straw (0.3 mg kg(-1)) and grain (0.06 mg kg(-1)) of barley compared to the control (0.6 and 0.2 mg kg(-1), respectively). In addition, red fescue grown in sludge-treated plots contained significantly higher levels of Al, Cu, Pb, As and Cr compared to the control. The levels of several metals in barley and red fescue grown in both treatments exceeded background values found in the literature. The Cu content in barley straw exceeded 100 mg kg(-1) in both treatments and might be toxic to grazing animals. Thus, this study suggests that adding sewage sludge to the mine tailings at Aitik would not counteract the effects of the sulphide oxidation in the tailings. Furthermore, using a sequential extraction technique proved preferable to using total metal analysis in order to predict plant uptake of the elements in the tailings.     

Partitioning of trace metals before and after biological removal of metals from sediments

Metal removal by biological solubilization in three strongly contaminated sediments was carried out in a two-liter stirred bioreactor. Biological treatment yielded metal removal efficiencies in the range of 11-30%, 43-57%, 60-79%, 61-90%, 18-21%, 0-10% for Pb, Cu, Zn, Cd, Ni and Cr, respectively. The treated sediments were then rinsed with a NaCl solution (0.5 M), resulting in an increase by nearly 47% in Pb removal for the three sediments, while for other metals (Cu, Zn, Cd, Ni, Cr), the NaCl rinse did not seem to allow any significant increase in metal solubilization. A standard procedure of sequential selective extraction (SSE) was applied to the sediments before and after each treatment. With regard to Pb, Zn and Cd, the carbonate bound fractions (2/3 sediments) represented 18-42% of metals prior to treatment, while the iron and manganese oxides bound fraction constituted 39-60% of metals for the three sediments. Between 90 and 100% of Pb, Zn and Cd removed by the process came from the fractions bound to carbonates and from those bound to Fe and Mn oxides. The organic matter and sulfide bound fractions contained 65-72% of total Cu present before treatment and the process removed, on average, 63% Cu present in this fraction. In contrast, Ni and Cr were found mainly in the residual fractions (50-80%). Finally, this biological treatment did not solubilize Cr appreciably, while removal of Ni mostly originated from the carbonate and Fe/Mn oxides fractions (70-80%).     

Species of dissolved metals derived from oligotrophic hard water

By fractioning of dissolved organic carbon (DOC) and of associated metals Na, K, Mg, Ca, Al, Fe, Mn, Ni, Cr, Cu, Pb, Cd, and Zn according to the molecular sizes by means of gel chromatography in several stages, it could be shown that all metals, even the alkaline and alkaline earth metals, are, to a measurable degree, present in chelated form. This type of association covers 97.3% with Pb, 94.6% with Al, 91.5% with Cr, 82.2% with Fe of the total concentrations of each metal mentioned. About 69% of all metal chelates are represented by Mg-compounds. This may be caused by pre-treatment procedures, nevertheless the Mg-concentrations of the different DOC-fractions indicating to be one regulating factor for the uptake of other metals in the studied hard water. The chelated form was also obtained with Mn, Cd, Zn, and Mg, while with Cu, Ni, Na, Ca, and K there is an abundance of ionic forms.The metal distribution within the different molecular size fractions of the DOC proves the existence of specific distribution pattern for Pb and Mn: Pb is preferably chelated by macromolecular substances, whereas Mn combines mainly with minor ones. Cr seems to behave similar as Pb. Regulation' mechanisms for the different metal distribution patterns within the DOC-fractions as well as ecophysiological aspects of the results are discussed.