Wet Deposition of Trace Metals in Singapore

The concentrations of 12 trace metals (Al, Cd, Cr, Cu, Co, Fe,Mn, Ni, Pb, Zn, V, and Ti) in wet depositions are reported. Eighty four rainwater samples were collected using an automated wet-only sampler in Singapore for one year (2000) and subjected to chemical analysis using ICP-MS. Based on the volume-weighted meanconcentrations measured, the trace metals were classified into three groups: Al and Fe with an average concentration of largerthan 15 μg L^-1, Cr, Cu, Mn, Ni, Pb, Zn, V, and Ti withconcentrations between 1 and 10 μg L^-1, and finally Co and Cd with concentrations lower than 1 μg L^-1. Elementenrichment factors were calculated to distinguish between naturaland anthropogenic sources. The calculation of crustal enrichmentfactors with Al as the reference element indicated that while Ti,Fe and Mn originated from crustal sources, the remaining trace metals (Cd, Cr, Co, Cu, Ni, Pb, Zn and V) were mainly derived from anthropogenic sources. The removal of the trace metals from the atmosphere by precipitation was influenced by the rainfall amount as well as pH. The magnitude of the measured average annual wet deposition fluxes of Al, Fe, and combustion-generatedelements such as V, Ni, and Cu is higher than that reportedfor other sites outside Singapore, owing to abundant rainfallthroughout the year in this region.     

Enhanced Heavy Metal Phytoextraction from Marine Dredged Sediments Comparing Conventional Chelating Agents (Citric Acid and EDTA) with Humic Substances

Metal (Cu, Mn, Ni, Zn, Fe) concentrations in marine sediment and zooplankton were investigated in Izmir Bay of the Eastern Aegean Sea, Turkey. The study aimed to assess the levels of metal in different environmental compartments of the Izmir Bay. Metal concentrations in the sediment (dry weight) ranged between 4.26–70.8 μg g^?1 for Cu, 233–923 μg g^?1 for Mn, 14.9–127 μg g^?1 for Ni, 25.6–295 μg g^?1 for Zn, 12,404–76,899 μg g^?1 for Fe and 38,226–91,532 μg g^?1 for Al in the Izmir Bay. Maximum metal concentrations in zooplankton were observed during summer season in the inner bay. Significant relationships existed between the concentrations of certain metals (Al, Fe, Mn and Ni) in sediment, suggesting similar sources and/or similar geochemical processes controlling such metals. Higher concentrations of Cu, Zn and percent organic matter contents were found in the middle-inner bays sediments. Based on the correlation matrix obtained for metal data, organic matter was found to be the dominant factor controlling Cu and Zn distributions in the sediment. In general, mean Cu and Zn levels in the bay were above background concentrations in Mediterranean sediments. Zooplankton metal concentrations were similar to sediment distributions.     

Seasonal Variations in Vertical Redox Stratification and Potential Influence on Trace Metal Speciation in Minerotrophic Peat Sediments

Seasonal variations in pore water and solid phase geochemistry were investigated in urbanized minerotrophic peat sediments located in southwestern Michigan, USA. Sediment pore waters were collected anaerobically, using pore water equilibrators with dialysis membranes (“peepers”) and analyzed for pH, alkalinity, dissolved ΣPO₄ ^?3, ΣNH₄ ⁺, ΣS^?2, SO₄ ^?2, Fe⁺³, Fe⁺², and Mn⁺² at 1-2 cm intervals to a depth of 50 cm. Cores collected adjacent to the peepers during all four seasons were analyzed for reactive solid phase Fe according to extraction methods proposed by Kostka and Luther (1994). The association of Fe and trace metals (Mn, Pb, Zn, Cu, Cr, Co, Cd, U) with operationally defined solid phase fractions (carbonates, iron and manganese oxides, sulfides/organics and residual) was assessed for cores extracted during winter and spring using extraction methods proposed by Tessier et al. (1979, 1982). Pore water Fe and S data demonstrate a clear seasonal variation in redox stratification of these sediments. The redox stratification becomes more compressed in spring and summer, with relatively more reducing conditions closer to the sediment water interface (SWI), and less reducing conditions near the SWI in fall and winter. In the upper 10–15 cm of sediment, the pool of ascorbate extractable Fe, thought to be indicative of reactive Fe(III) oxides, diminishes during spring and summer, in agreement with seasonal changes in redox stratification indicated by the pore water data. Tessier extractions indicate that the total extractable quantity of all metals analyzed in this study decrease with depth, and that the majority of the non-residual Fe, Pb, Zn, Cu, Cr, Co, Cd, and U is typically associated with the sulfide/organic fraction of the sediments at all depths. Non-residual Mn, in contrast, is significantly associated with carbonates in the upper 15–25 cm of the sediment, and predominantly associated with the sulfide/organic fraction only in deeper sediments.     

Relationships of Heavy Metals in Natural Lake Waters with Physico-chemical Characteristics of Waters and Different Chemical Fractions of Metals in Sediments

The relationships between heavy metal concentrations and physico-chemical properties of natural lake waters and also with chemical fractions of these metals in lake sediments were investigated in seven natural lakes of Kumaun region of Uttarakhand Province of India during 2003–2004 and 2004–2005. The concentrations of Cr, Mn, Fe, Ni, Cu, Zn, Cd and Pb in waters of different lakes ranged from 0.29–2.39, 10.3–38.3, 431–1407, 1.0–6.6, 5.3–12.1, 12.6–166.3, 0.7–2.7 and 3.9–27.1 μg l^?1 and in sediments 14.3–21.5, 90.1–197.5, 5,265–6,428, 17.7–45.9, 13.4–32.0, 40.0–149.2, 11.1–14.6 and 88.9–167.4 μg g^?1, respectively. The concentrations of all metals except Fe in waters were found well below the notified toxic limits. The concentrations of Cr, Mn, Ni, Cu, Zn, Cd and Pb were positively correlated with pH, electrical conductivity, biological oxygen demand, chemical oxygen demand and alkalinity of waters, but negatively correlated with dissolved oxygen. The concentrations of Cr, Ni, Zn, Cd and Pb in waters were positively correlated with water soluble + exchangeable fraction of these metals in lake sediments. The concentrations of Zn, Cd and Pb in waters were positively correlated with carbonate bound fraction of these metals in lake sediments. Except for Ni, Zn and Cd, the concentrations of rest of the heavy metals in waters were positively correlated with organically bound fraction of these metals in lake sediments. The concentrations of Cr, Mn, Ni, Cu and Zn in waters were positively correlated with reducible fraction of these metals in lake sediments. Except for Cd, the concentrations of rest of the metals in waters were positively correlated with residual fraction and total content of these heavy metals in lake sediments.     

Dissolved and Particulate Metals in the Mero River (NW Spain): Factors affecting Concentrations and Load during Runoff Events

This article examines the metal [aluminum (Al), iron (Fe), manganese (Mn), copper (Cu), and zinc (Zn)] runoff dynamics in the Mero River (northwestern Spain). At the catchment outlet, metal concentrations, suspended solids, dissolved organic carbon, pH, and discharge were determined during three runoff events. The river drains an agroforestry catchment of 65 km² with relatively high livestock density. Dissolved and particulate metal concentrations increased during the events with respect to pre-event concentrations, but the increase of the dissolved fraction is relatively small compared to that of the particulate fraction. The dissolved metal concentration peaks appeared after the hydrograph peak, suggesting transport associated with subsurface flow. For particulate metals, peaks usually occurred during the falling limb of hydrograph, implying distant-river source of metals. Particulate forms represented more than 90% of total Al, Fe, and Mn load, whereas for Cu and Zn its contributions were 52–76% and 31–56%, respectively. The high positive correlations of all particulate metals, except Zn, with suspended solid concentrations indicate that these constituents play a major role in transport of metals. Soil erosion is the main process responsible for causing elevated Al, Fe, and Mn concentrations in the river during rainfall–runoff events while Zn and Cu come mainly from the addition of slurries and manures to farmland.     

Increasing the Knowledge of Heavy Metal Contents and Sources in Agricultural Soils of the European Mediterranean Region

This paper contributes to increase the knowledge of the contents and sources of heavy metals (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn) to agricultural soils in Castellón province (Spain), a representative area of the European Mediterranean region. The surface horizons of 77 agricultural soils under vegetable crops were sampled and heavy metals were analysed by atomic absorption spectroscopy (AAS) after microwave extraction using the USEPA 3051A method. Mean heavy metal contents were similar to those obtained in other areas of this region. However, heavy metal contents (e.g. Cr, Pb) in some soils were above the maximum limit set in the 86/278/CEE Directive. Multivariate analysis (correlation analysis and principal component analysis – PCA) was performed so as to identify the sources of heavy metals to soils. Co, Fe and Ni were highly correlated amongst them (r?>?0.800; p?<?0.01), whereas Cr and Mn were less correlated with Co, Fe and Ni (r?>?0.500; p?<?0.01). Other relationships among heavy metals (i.e. Cu, Pb and Zn) were also identified, although correlation coefficients were not so high as those among Co, Fe and Ni (r?<?0.500; p?<?0.01). Contents of Co, Fe, Mn and Ni were interpreted to be mainly associated with parent rocks corresponding to the first principal component (PC1). On the other hand, Cd, Cu, Pb and Zn were interpreted to be mainly related to anthropogenic activities and comprised the second (Pb and Zn) and the third (Cd and Cu) principal components (PC2 and PC3, respectively), designated as anthropogenic components. Remarkably, Cr appears to be related in the study area to both the lithogenic and the anthropogenic components. Lithogenic elements were highly correlated with soil properties. Positive relationships with CEC (r?>?0.200; p?<?0.05) and clay (r?>?0.400; p?<?0.01), and negative relationships with carbonates (r?>??0.400; p?<?0.01) and sand (r?>??0.300; p?<?0.01) were observed. Anthropogenic elements were less correlated with soils properties, since these elements are generally more mobile because they form more soluble chemical species associated to anthropogenic sources. Particularly, no correlation was found between Cd and Zn and soil properties. These findings extend results achieved in other parts of the region, highlighting the need to set soil quality standards in order to declare soils affected by anthropogenic pollution, particularly in the case of anthropogenic metals such as Cd, Cu and Pb, and also Cr and Zn in some areas. Further knowledge from other areas in this region would improve the basis for proposing such standards at regional level, which is a priority objective in Europe according to the European Thematic Strategy for Soil Protection.     

Metal Extractability in Binary and Multi-metals Spiked Calcareous Soils

In the present study, a laboratory experiment was designed to compare the 0.01 M calcium chloride (CaCl₂) and diethylenetriaminepentaacetic acid (DTPA) extraction methods for their ability to predict cadmium (Cd), copper (Cu), iron (Fe), Manganese (Mn), nickel (Ni), and zinc (Zn) availability and mobility in five calcareous soils. The soils were spiked with different amounts of metals (0, 50, 100, 200, and 400 mg kg^?1) both in binary (Cu and Zn; Ni and Cd; Fe and Mn) and in multi-systems (Cd, Cu, Fe, Mn, Ni, and Zn) and incubated for 1 months at field capacity. In metal-spiked soils, both extraction methods showed a linear relationship of extractable to total metals for all soils. The fraction of total metals extracted by DTPA was much higher than the fraction extracted by CaCl₂, which was attributed to the formation of soluble metal-complexes in the complexing extracts calculated by the Visual Minteq program. DTPA extraction method showed higher selectivity for Cu over other metals both in binary and in multi-systems. Different order of metals extractability was found in binary and multi-systems for both extraction methods. Solid/solution distribution coefficient (K_d) was calculated by the ratio of the solid phase to soil solution concentration of metals extracted by CaCl₂ or DTPA extraction methods. Both in binary and in multi-systems, the average K_d (l kg^?1) of metals by soils were in the order of Mn (5398) > Fe (4413) > Zn (3376) > Cu (2520) > Ni (969) > Cd (350) in the CaCl₂-extractable metals and Fe (35) ≥ Ni (34) > Zn (18) > Mn (11.2) > Cu (6.3) > Cd (4) in the DTPA-extractable metals. Results showed that among the six studied metals, Cd had the lowest K_d, implying a relative higher mobility in these calcareous soils. The Visual Minteq indicated that in the CaCl₂-extraction method and in both binary and multi-systems the dominant species for Cu, Mn, Ni, and Zn were Cu²⁺, Mn²⁺, Ni²⁺ and Zn²⁺, respectively, while for Cd and Fe, the dominant species were CdCl⁺ and Fe(OH)²⁺, respectively.     

Evaluation of Loads and Sources of Heavy Metals in Tama River, Tokyo

The loads and sources of heavy metals (Cd, Co, Cu, Mn, Mo, Ni, Pb, V, and Zn) in the midstream of Tama River were evaluated on the basis of their chemical analyses in ordinary and stormwater runoff from July 2007 to November 2008. Tama River is one of the three major rivers flowing into Tokyo Bay. The total annual water discharges differed largely for 2007 and 2008, depending on the scales of typhoon rainfalls and other heavy rainfalls in each year. The concentrations of the metals other than Mo in the river did not change markedly at a flow rate of less than approximately 200 m³ s^?1, but at higher flow rates, the concentrations of all the metals increased linearly with the increase in the log of flow rate (r ²?=?0.94–0.99). The annual loads of heavy metals for 2007 and 2008 were estimated using regression equations between the above parameters and the hourly flow rate data for each year. For the metals other than Mo, the contribution of the loads at higher flow rates (>200 m³ s^?1) was much larger than that at lower flow rates (<200 m³ s^?1), showing the importance of the particulate loads (primarily crustal materials) during storm runoff following typhoon rainfalls and other heavy rainfalls. In contrast, the loads of Mo at lower flow rates accounted for major portions (56–78%) of the total loads, because of a relatively small contribution of particulate load during storm runoff. The contribution of the loads of Mo, Zn, Cd, Cu, and Ni at lower flow rates to the annual loads was larger than that of other metals. It was found that the concentrations of these metals in ordinary runoff are strongly affected by the discharge of treated water from sewage treatment plants which are located along the catchment. Thus, treated water from sewage treatment plants may be the primary source contributing to the present pollution of Mo, Zn, Cd, Cu, and Ni in Tokyo Bay.     

Heavy Metals in Freshly Deposited Stream Sediments of Rivers Associated with Urbanisation of the Ganga Plain,India

Freshly deposited stream sediments from six urban centres of the Ganga Plain were collected and analysed for heavy metals to obtain a general scenery of sediment quality. The concentrations of heavy metals varied within a wide range for Cr (115–817), Mn (440–1 750), Fe (28 700–61 100), Co (11.7–29.0), Ni (35–538), Cu (33–1 204), Zn (90–1 974), Pb (14–856) and Cd (0.14–114.8) in mg kg^-1. Metal enrichment factors for the stream sediments were <1.5 for Mn, Fe and Co; 1.5–4.1 for Cr, Ni, Cu, Zn and Pb; and 34 for Cd. The anthropogenic source in metals concentrations contributes to 59% Cr, 49% Cu, 52% Zn, 51% Pb and 77% Cd. High positive correlation between concentrations of Cr/Ni, Cr/Cu, Cr/Zn, Ni/Zn, Ni/Cu, Cu/Zn, Cu/Cd, Cu/Pb, Fe/Co, Mn/Co, Zn/Cd, Zn/Pb and Cd/Pb indicate either their common urban origin or their common sink in the stream sediments. The binding capacity of selected metals to sediment carbon and sulphur decreases in order of Zn > Cu > Cr > Ni and Cu > Zn > Cr > Ni, respectively. Stream sediments from Lucknow, Kanpur, Delhi and Agra urban centres have been classified by the proposed Sediment Pollution Index as highly polluted to dangerous sediments. Heavy metal analysis in the <20-μm-fraction of stream sediments appears to be an adequate method for the environmental assessment of urbanisation activities on alluvial rivers. The present study reveals that urban centres act as sources of Cr, Ni, Cu, Zn, Pb and Cd and cause metallic sediment pollution in rivers of the Ganga Plain.     

Annual and Seasonal Variations of Trace Metals in Atmospheric Suspended Particulate Matter in Islamabad, Pakistan

Total Suspended particulate matter (TSP) in urban atmosphere of Islamabad was collected using a high volume sampling technique for a period of one year. The nitric acid–perchloric acid extraction method was used and the metal contents were estimated by atomic absorption spectrophotometer. The highest mean concentration was found for Ca at 4.531 µg/m³, followed by Na (3.905 µg/m³), Fe (2.464 µg/m³), Zn (2.311 µg/m³), K (2.086 µg/m³), Mg (0.962 µg/m³), Cu (0.306 µg/m³), Sb (0.157 µg/m³), Pb (0.144 µg/m³) and Sr (0.101 µg/m³). On an average basis, the decreasing metal concentration trend was: Ca > Na > Fe > Zn > K > Mg > Cu > Sb > Pb > Sr > Mn > Co > Ni > Cr > Li > Cd ≈ Ag. The TSP levels varied from a minimum of 41.8 to a maximum of 977 µg/m³, with a mean value of 164 µg/m³, which was found to be higher than WHO primary and secondary standards. The correlation study revealed very strong correlations (r?>?0.71) between Fe–Mn, Sb–Co, Na–K, Mn–Mg, Pb–Cd and Sb–Sr. Among the meteorological parameters, temperature, wind speed and pan evaporation were found to be positively correlated with TSP, Ca, Fe, K, Mg, Mn and Ag, whereas, they exhibited negative relationships with relative humidity. On the other hand, Pb, Sb, Zn, Co, Cd and Li revealed significant positive correlations with relative humidity and negative with temperature, wind speed and pan evaporation. The major sources of airborne trace metals identified with the help of principle component analysis and cluster analysis were industrial emissions, automobile exhaust, biomass burning, oil combustion, fugitive emissions, resuspended soil dust and earth crust. The TSP and selected metals were also studied for seasonal variations, which showed that Na, K, Zn, Cu, Pb, Sb, Sr, Co and Cd peaked during the winter and remained lowest during the summer, while Ca, Fe, Mg and Mn were recorded highest during the spring.     

Influence of Acidification and Liming on the Distribution of Trace Elements in Surface Waters

Metals in water have been monitored for up to 18 years in acidified regions of Sweden. The concentrations of metals (Al, Cd, Cu, Fe, Mn, Mo, Pb, Zn) were determined by AAS and ICP-MS, the dissolved fractions after separation by in-situ dialysis. Elements showing negative pH-correlation were primarily Al, Zn, Cd, Mn, and Pb, while Mo was positively correlated to pH, indicating a predominance of negatively charged ionic forms. Zn, Cd, and Mn occurred primarily in the dissolved fractions, especially at the lower pH levels. Fe, Al, Pb and Mn were further enriched in humic waters. During the study period, some of the sites were subject to lime treatment, which had a marked influence on most elements, causing the mean levels and the seasonal fluctuations to decrease. Treatment on the lake surface was less effective than wetland liming to reduce seasonal fluctuations, especially for metals mainly originating from the catchments, as Fe and Al.     

Atmospheric deposition of heavy metals in central Ontario

As part of a study to determine the magnitude of atmospheric inputs of materials into the lakes of central Ontario, a four-station network of bulk deposition and wet-only precipitation samplers was established in the Muskoka-Haliburton and Sudbury regions to determine the deposition (mg m^2? yr^?1) and volume weighted concentration (μg 1^?1) of Ph, Cu, Ni, Zn, Al, Mn and Fe in precipitation. Large temporal variations in the monthly deposition of all metals were observed. The variations for Cu and Ni exhibited seasonal patterns which could be attributed to a combination of source and wind direction factors. Concentration and deposition of all metals at Muskoka-Haliburton were generally as low or lower than median North American values from the literature. At Sudbury, the large local smelting industry contributed to the elevated Cu, Ni, Zn, and Fe deposition measured in the region (up to two orders of magnitude larger than Muskoka-Haliburton); Al and Mn values were not elevated. Deposition of Cu. Ni and Fe was inversely related to distance from the largest point source at Sudbury. The importance of dry deposition is greatest at Sudbury where dry inputs of Cu, Zn, Al, and Fe generally exceed wet inputs. In contrast, wet deposition of metals at Muskoka-Haliburton predominates over dry. Calculation of an enrichment factor (normalized against Mn) showed that the levels of Pb, Cu, Ni and Zn observed in the precipitation of central Ontario require an additional non-crustal source (either natural or anthropogenic) for explanation.     

Assessing the Influence of Different Atmospheric and Soil Mercury Concentrations on Foliar Mercury Concentrations in a Controlled Environment

This study vividly presents results from a seasonal particulate matter measurement campaign conducted at world’s largest ship-breaking yard i.e., Alang-Sosiya (Gujarat, India) at six locations and a reference station at Gopnath which is 30 km south of this ship-breaking yard. The collected suspended particulate matter (SPM) 24-h samples were critically analyzed for heavy metals (Pb, Cd, Co, Ni, Cr, Mn, Fe, Cu, Zn). The average concentration of SPM within the ship-breaking yard during the investigation was 287.5 ± 20.4 μg m^?3 and at reference station it was 111.13 ± 5.81 μg m^?3. These values are found to be in excess of the permitted national standards. The levels of heavy metals at Alang-Sosiya are very high as compared to US EPA and WHO guidelines. The mean concentrations of all metals are in the order: Fe >>Zn >Cu > Mn > Cd >Pb > Co >Ni >Cr. The results on enrichment factors (EF) suggest that most of the metals in the ship-breaking yard exhibit EF values of near or above 100 which must have been comprehensively affected by ship-breaking activities. Metal data was used to evaluate the role of spatial factors on their distribution characteristics. Thereafter, factor analysis was carried out to identify the main components liable for the variance of the data set.     

Accumulation of Metals in the Sediment and Reed Biomass of a Combined Constructed Wetland Treating Domestic Wastewater

This study assessed the accumulation of Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn in the sediment and biomass of P. australis (Cav.) Trin. ex Steud. in a combined constructed wetland (CW) designed for the treatment of domestic wastewater of 750 population equivalents. The CW consists of two vertical subsurface flow (VSSF) reed beds followed by two horizontal subsurface flow (HSSF) reed beds. The sediment in the VSSF reed bed was contaminated with Cu (201 ?±? 27 mg kg^?1 DM) and Zn (662 ?±? 94 mg kg^?1 DM) after 4 years of operation. Concentrations of Cd, Cu, Pb and Zn in the sediment generally decreased along the treatment path of the CW. On the contrary, higher Al, Cr, Fe, Mn and Ni concentrations were observed in the sediment of the inlet area of the HSSF reed bed. Redox conditions were presumably responsible for this observed trend. Metal concentrations in the reed biomass did not show excessive values. Accumulation in the aboveground reed biomass accounted for only 0.5 and 1.4% of, respectively, the Cu and Zn mass load in the influent. The sediment was the main pool for metal accumulation in the CW.     

After effects of metals derived from a highly metal-polluted sludge on maize (Zea mays L.)

High Cd and Ni concentrations in sandy soils were built up in a field experiment, receiving an unusually metal-polluted sewage sludge between 1976 and 1980, at Bordeaux, France. The study evaluates the availability of metals and their after effects on maize at one point in time, the 8th year following termination of sludge application (1988). Plant parts (leaves, stalks, roots, grains) and soil samples were collected from plots which received 0 (Control), 50 (S1) and 300 Mg sludge DW ha^?1 (S2) as cumulative inputs. Dry-matter yield, plant metal concentrations, total, and extractable metals in soils were determined. Metal inputs resulted in a marked increase in total and extractable metals in soils, except for extractable Mn and Cu with either 0.1 N Ca(NO₃)₂ or 0.1 N CaCl₂. Total metal contents in the metal-loaded topsoils (0–20 cm depth) were very often lower, especially for Cd, Zn, and Ni, than the expected values. Explanation was partly given by the increases of metal contents below the plow layer, particularly for Cd at the low metal loading rate, and for Cd, Ni, and Cu at the high one (Gomez et al., 1992). In a control plot beside a highly metal- polluted plot, Cd, Zn, and Ni concentration in soil increased whereas the concentration of other metals was unchanged; lateral movement, especially with soil water, is plausible. Yield of leaves for plants from the S2 plot was reduced by 27%, but no toxicity symptoms developed on shoots. Yields of stalks for plants in both sludge-treated plots numerically were less than the controls but the decrease was not statistically significant. Cd and Ni concentrations increased in all plant parts with metal loading rate while Mn concentrations decreased. Leaf Cd concentration in plants from sludge-treated plots (i.e. 44 and 69 mg Cd kg^?1 DM for S1 and S2) was above its upper critical level (i.e. dry matter yield reduced by 10%: 25μg Cd g^?1 DM in corn leaves, Macnicol and Beckett, 1985). Yield reduction at the high metal-loading rate was probably due to 3 main factors: Mn deficiency in leaves, the accumulation of Ni especially in roots, and the increase of Cd in leaves. The amount of metal taken up by plants from the control plot ranked in the following order (mole ha^?1): Fe(22)? Mn(7)>Zn (5.6)?Cu (0.7), Ni (0.6), Cd (0.4). For sludge-treated plots, the order was (values for S1 and S2 in mole ha ^?1): Fe (16, 15)>Zn (7.9, 7.7)>Ni (4.3, 4.7)>Cd (1.9, 2.1)>Cu (1.0,1.2), Mn (1.5, 1.1). Zn and Cd had the greatest offtake percent from the soil to the above ground plant parts. Cd or Ni uptake by maize were correlated with extractable metals by unbuffered salts (i.e. 0.1 N Ca(NO₃)₂ and 0.1 N CaCl₂). It is concluded that part of the sludge-borne Cd and Ni can remain bioavailable in this sandy soil for a long period of time (e.g. 8 yr) after the termination of metal-polluted sludge application.     

Solid-Solution Metal Partitioning for the Upper Mero River Basin (NW Spain)

This study determines the seasonal variability of metal partition coefficients [aluminium (Al), iron (Fe), manganese (Mn), copper (Cu), and zinc (Zn)] and analyses the importance of suspended sediments (SS), dissolved organic carbon (DOC) concentrations, pH, and discharge (Q) on the seasonal variability of metal partition coefficients (K_Ds) in the headwaters of the Mero River catchment, which drains an agroforestry area in northwestern Spain. Metal partition coefficients were used as an approach to relate dissolved and particulate fractions. Water samples were collected over 3 years (2005–2008) at the catchment outlet. The mean metal dissolved concentrations were: Fe (43.5 μg L^?1) > Al (23.3 μg L^?1) > Zn (1.8 μg L^?1) > Mn (1.2 μg L^?1) > Cu (0.3 μg L^?1). Partition coefficients followed the order Mn > Al > Fe > Zn > Cu, and their values exhibited low variability. Al, Cu, and Zn partition coefficients presented the greatest values in summer, except during 2007–2008, when the greatest K_Ds value was observed in autumn, whereas the K_Ds of Fe showed the greatest values in winter. The K_D of Mn has no seasonality. For Al, Cu, and Zn, the seasonal SS concentrations were closely related to Kd. For Fe, Kd was more closely related to DOC concentration than to SS concentration.     

Behavior of Metals Under Different Seasonal Conditions: Effects on the Quality of a Mexico–USA Border River

Spatial and seasonal mobilization trends of metals in surface water were evaluated in the US–Mexico San Pedro River (SPR). Water samples were collected at five sampling stations for the analysis of dissolved oxygen, pH, electric conductivity, sulfates, and metals (Cd, Cu, Fe, Mn, Pb, and Zn). Quality of the water was characterized through Ecological Criteria of Water Quality (ECWQ) established in Mexico and Water Quality Criteria (Environmental Protection Agency (EPA)). High total metal concentrations were detected as follows: Fe?>?Cu?>?Mn?>?Zn?>?Pb?>?Cd. Metal concentrations were slightly higher in dry season than in rainy season: Cd (below detection limit (BDL)–0.21 mg L^?1), Cu (BDL–13 mg L^?1), Fe (0.16–345 mg L^?1), Mn (0.12–52 mg L^?1), Pb (BDL–0.48 mg L^?1), and Zn (0.03–17.8 mg L^?1). Low pH and dissolved oxygen values as well as high sulfate content were detected in both seasons. High values of metals (Cd, Cu, Fe, Mn, Pb, Zn) were detected at station E1 representing pollution source, as well as at stations E2 (Cd, Cu, Fe, Mn), E3 (Fe, Mn, Pb), and E4 and E5 (Fe, Mn). Detected concentrations exceeded maximum permissible established in ECWQ and Water Quality Criteria (EPA). Efflorescence salts on sediments in the dry season could increase levels of metals in water column. This study provides valuable information on the potential mobility of metals in surface water of SPR located in an arid environment where transport processes are strongly linked to climate. The information derived from this study should help the regional and national authorities to address present environmental regulations.     

Influence of prolonged use of sewage effluent in irrigation on heavy metal accumulation in soils and plants

Total content of Fe, Mn, Zn, Cu, Pb, Cd, Ni and Co in soils irrigated with sewage effluent increased with increasing years of using sewage effluent in irrigation. Iron and Co applied to the soil from sewage effluent were immobilized mainly in unavailable form; Pb, Cd, and Ni in moderately available form; and Mn, Zn, and Cu in highly available form. The concentrations of Fe, Mn, Zn and Cu in tops of alfalfa and leaves of corn grown on these soils increased substantially with increased levels of available metal content of the soil, while those of other metals were little affected. As for orange, continuous increase in leaves metal content with time was found for Fe, Mn, Zn, Co and Cd. The concentrations of Cd, Co, Ni and Pb in corn grains and orange fruits were several times higher than normal, and this reduces their suitability for human consumption.     

Leaching of Metals from Oxidising Sulphide Mine Tailings with and without Sewage Sludge Application

A 20-month column experiment investigated leaching of Al, Cu, Mn, Ni, Zn, Cd and Pb during sulphide oxidation in mine tailings with and without sewage sludge (SS) amendment. Leachate pH decreased gradually in all columns during the experiment, irrespective of treatment, due to sulphide oxidation. As the degree of sulphide oxidation, and thus the pH trajectory, differed between replicates (n?=?3), running data for each column used are reported separately and the relationships between sulphide oxidation, metal leaching and treatment in each column compared. Mean pH in the columns correlated negatively with total amounts of leached SO₄ ^2-. In the beginning of the experiment the leachate concentrations of Al, Cu, Zn, Ni and Pb were higher in SS-treated columns due to high initial concentrations of dissolved organic carbon. As leaching proceeded, however, the amounts of Al, Cu, Mn and Ni leached from the columns were closely related to the degree of sulphide oxidation in each column, i.e. to its mean pH. There were no statistically significant differences between treatments regarding the total amounts of metals leached and thus addition of sewage sludge to the tailings appeared to play a minor role for metal leaching patterns. Peak concentrations of Al and Cu in the leachate from untreated tailings and of Zn in the leachate from both untreated and SS-treated tailings at pH 4 exceeded national background values for groundwater.     

Fluctuations of element concentrations during the growing season of Polytrichum formosum (Hedw.)

Fourteen elements (Al, Ba, Ca, Cd, Cr, Cu, Fe, K, Mg, Ni, Pb, Sr, Ti, and Zn) were quantitatively determined by AES/ICP in aboveground parts of the endohydric moss Polytrichum formosum (Hedw.) after sampling over regular intervals from 1985 to 1987. With the exception of K, Mg, and Zn all elements showed a large continuous fluctuation (> 30%) during the growing season. Four different patterns of seasonal variation were found: (1) large seasonal variations of element concentrations (～80%) with maximum concentrations in winter and lowest concentrations in the summer months (Al, Fe, Cr, Mg, Pb, and Ti), (2) smaller seasonal variations (～50%) with maximum concentrations in winter and lowest concentrations in summer (Ba, Ca, Cd, Cu, Sr), (3) slight seasonal variations (～30%) with maximum concentrations in the summer (K), and (4) slight seasonal changes (～30%) with maximum concentrations in the winter (Mg and Zn). The relative biological variance of element concentrations between 9 different stands of Polytrichum formosum decreases in the following sequence: Ti, Al, Pb, Fe, Cr, Ni, Ba, Ca, Cu, Cd, K, Mg, Sr, Zn. The relative biological variance of individual elements is generally lower than the variance in element concentrations caused by seasonal changes. Because of its high biological variance for most elements investigated (seasonal as well as between different stands of Polytrichum formosum) this moss should only be used as a passive bioindicator, if all other environmental parameters are standardized.