Chemistry and adsorption-desorption properties of manganese oxides deposited in Forehill Water Treatment Plant,Grampian, Scotland

Manganese oxide coatings on sand particles within filtration beds from a water treatment plant in Grampian, Scotland were examined to determine their control on metal mobility. This study first sought to characterise the oxides, notably their mineralogy and metal content, to provide a foundation for studies on the adsorption of dissolved metals from the treated water by the oxides. The oxides were examined by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and analysed by flame atomic absorption spectrophotometry (AAS). These techniques showed the oxide coatings were amorphous but uniformly distributed over each sand grain. The oxides were selectively removed from the sand grains prior to analysis by AAS using a hydroxylamine hydrochloride selective leaching method. The compositional range of the extracts was 100–150 mg L⁻¹ Mn; 30–55 mg L⁻¹ Fe; 17–56 mg L⁻¹ Ca; 4.6–7.0 mg L⁻¹ Ni; 4.6–6.8 mg L⁻¹ Zn and 1.3–5.7 mg L⁻¹ Mg. When these results are expressed as mg of metal per mg of Mn, the metal content of the oxides is remarkably uniform: 0.25–0.37 mg Fe; 0.14–0.35 mg Ca; 0.035–0.042 mg Ni; 0.035–0.040 mg Zn; 0.01–0.04 mg Mg. The greatest metal concentrations were consistently found in the upper 3 cm of the filtration bed, and these decrease with increasing depth. After the beds are cleaned a more uniform distribution of metals occurs throughout the bed. The metals taken up by the manganese coating are retained over a wide pH range with the exception of Ca and Mg which desorb to a significant extent. The percentage of calcium and magnesium lost from the coating ranges from 30–94%, the amount being dependent on the final pH of the solution. The presence of manganese oxide in the filtration beds appears to be advantageous in terms of removal of transition metals from the treated water.     

Bioavailability of trace metals in brownfield soils in an urban area in the UK

Thirty-two brownfield sites from the city of Wolverhampton were selected from those with a former industrial use, wasteland or areas adjacent to industrial processes. Samples (<2 mm powdered soil fraction) were analysed, using inductively coupled plasma–atomic emission spectrometry (ICP–AES) for 20 elements. Loss on ignition and pH were also determined. A five-step chemical sequential extraction technique was carried out. Single leach extraction with 0.12 M hydrochloric acid of Pb, Cu and Zn in soil was determined as a first approximation of the bioavailability in the human stomach. Some of the sites were found to have high concentrations of the potentially toxic elements Pb, Zn, Cu and Ni. The partitioning of metals showed a high variability, however a number of trends were determined. The majority of Zn was partitioned into the least chemically stable phases (steps 1, 2 and 3). The majority of Cu was associated with the organic phase (step 4) and the majority of Ni was fractionated into the residue phase (step 5). The majority of Pb was associated with the residue fraction (step 5) followed by Fe–Mn oxide fraction (step 3). The variability reflects the heterogeneous and complex nature of metal speciation in urban soils with varied historic histories. There was a strong inverse linear relationship between the metals Ni, Zn and Pb in the readily exchangeable phase (step 1) and soil pH, significant at P < 0.01 level. There was a significant increase (P < 0.05) in the partitioning of Cu, Ni and Zn into step 4 (the organic phase) in soils with a higher organic carbon content (estimated by loss on ignition). Copper was highly partitioned into step 4 as it has a strong association with organics in soil but this phase was not important for the partitioning of Ni or Zn. The fractionation of Ni, Cu and Zn increased significantly in step 3 when the total metal concentration increases (P < 0.01). The Fe–Mn oxide fraction becomes more important in soils elevated in these metals, possibly due to the scavenging of metals by oxides. Cu and Pb extracted by HCl was statistically similar to the sum of the metals in steps 1 to 4 (P < 0.01) and HCl available Zn was statistically similar to the sum of Zn in steps 1 to 3 (P < 0.01). Step 4 (the organic phase) was not an important phase for Zn, so it was concluded that any Cu, Zn and Pb present in soil in a nonresidue phase would be potentially available for uptake into the human system once soil has been ingested.     

Comparative study of the fate and mobility of metals discharged in mining and urban effluents using sequential extractions on suspended solids

The fate, bioavailability and environmental impacts of metals discharged in municipal and mining wastewater discharge will depend to a large extent on chemical speciation and distribution. Previous studies on metal bioaccumulation have shown that total metal concentrations are not a good predictor of bioavailability in the dispersion plumes of municipal effluents. The objective of this study was to determine the solid phase speciation of metals in surface waters receiving urban and mining effluents in order to assess their fate and relative mobility in the receiving environment. Suspended particulate matter was sampled using sediment traps at several sites downstream of effluent outfall plumes as well as at reference upstream sites. Particulate metal in operationally defined fractions—exchangeable/carbonates, reducible, oxidisable and residual—were determined in suspended particulate matter with a series of selective chemical extractions. Metal enrichment in suspended particles was generally observed in both mining and urban effluent discharges. When compared to its receiving environment, the mining effluent appeared to release more particulate metals (Cu, Fe, Zn) in the most reactive fractions (i.e. exchangeable/carbonates + reducible forms, 23–43%), while other released metals, such as Cd and Mn, were predominantly in the least reactive forms (i.e., oxidisable + residual, 73–97%). In contrast, the reactivity of all particulate metals, with the exception of Mn, from the urban effluent was much higher, with up to 65, 42, 30 and 43% for Cd, Cu, Fe and Zn, respectively, in the two most reactive fractions. As expected in effluent dispersion plumes, parameters such as the organic carbon, Fe oxide and carbonate contents have specific effects on the partitioning of several trace metals, particularly Cd, Cu and Zn. Our results indicated that the relative distributions of metals among geochemical fractions varied in the effluent receiving waters where organic carbon and Fe oxides appeared as the most important parameters. This could therefore decrease the exposure for aquatic organisms that are exposed to those contaminated sediments as well as the risk to human health.     

Geochemistry of leachates from the El Fraile sulfide tailings piles in Taxco, Guerrero, southern Mexico

Leachates from the El Fraile tailings impoundment (Taxco, Mexico) were monitored every 2 months from October 2001 to August 2002 to assess the geochemical characteristics. These leachates are of interest because they are sometimes used as alternative sources of domestic water. Alternatively, they drain into the Cacalotenango creek and may represent a major source of metal contamination of surface water and sediments. Most El Fraile leachates show characteristics of Ca–SO₄, (Ca+Mg)–SO₄, Mg–SO₄ and Ca–(SO₄+HCO₃) water types and are near-neutral (pH=6.3–7.7). Some acid leachates are generated by the interaction of meteoric water with tailings during rainfall events (pH=2.4–2.5). These contain variable levels of SO₄ ²⁻ (280–29,500 mg l⁻¹) and As (<0.01–12.0 mg l⁻¹) as well as Fe (0.025–2352 mg l⁻¹), Mn (0.1–732 mg l⁻¹), Zn (<0.025–1465 mg l⁻¹) and Pb (<0.01–0.351 mg l⁻¹). Most samples show the highest metal enrichment during the dry seasons. Leachates used as domestic water typically exceed the Mexican Drinking Water Guidelines for sulfate, hardness, Fe, Mn, Pb and As, while acidic leachates exceed the Mexican Guidelines for Industrial Discharge Waters for pH, Cu, Cd and As. Speciation shows that in near-neutral solutions, metals exist mainly as free ions, sulfates and bicarbonates, while in acidic leachates they are present as sulfates and free ions. Arsenic appears as As^(V) in all samples. Thermodynamic and mineralogical evidence indicates that precipitation of Fe oxides and oxyhydroxides, clay minerals and jarosite as well as sorption by these minerals are the main processes controlling leachate chemistry. These processes occur mainly after neutralization by interaction with bedrock and equilibration with atmospheric oxygen.     

Exposure to Selected Heavy Metals Through Water Ingestion in an Area Under the Influence of Tanneries

This study evaluated the potential toxicological risk posed to human health due to the exposure to heavy metals by water ingestion in an area affected by tanneries – the Cadeia-Feitoria hydrographic basin (Brazil). River water was collected at 10 sites, every 3 months, from July 1999 to April 2000. After acid digestion, total metal concentration was determined by inductively coupled plasma optical emission spectrometry (Cd, Cu, Cr, Ni, Zn), flame atomic absorption (Al, Fe, Pb, Mn), or cold vapor atomic absorption spectrometry (Hg). Cr(VI) was complexed with diphenyl-carbazide and detected by UV–vis spectrometry. In order to quantify the risk of exposure, the risk assessment methodology employed by the Environmental Protection Agency of the United States was applied at a screening level. The assumed scenarios included extreme exposure patterns (ingestion of untreated water, conversion of Cr(III) to Cr(VI), temporal peaks of pollution). Fe, Al, Cd, Hg, and Pb were not included in the risk analysis, since they showed a low toxicity potential or were undetected in the samples. The selected metals presented Hazard Quotients < 1, in the following order of increasing risk: Cu < Cr(III) < Zn < Ni < Mn < Cr(VI). Hazard indexes, representing the additive effect of contaminants, were also low in the basin (< 1), but comparatively increased in the lower reach of Feitoria and Cadeia Rivers. Although noncarcinogenic risk levels did not suggest possible adverse toxicological effects to the human population, a considerable deviation from background conditions was observed downstream the area where tanneries are mainly located.     

Metal fractionation of cadmium, lead and arsenic of geogenic origin in topsoils from the Marrancos gold mineralisation, northern Portugal

The Marrancos gold mineralisation has a chemical assemblage of Fe–As–Se–Bi–Au–Ag–Te–(Cu–Pb–Zn–Sn–W). The −200 mesh of 144 topsoil samples was analysed by ICP–MS to determine total contents of 53 elements that include potentially harmful elements like Cd, As and Pb. The soil geochemistry shows that some trace elements occur in considerably high concentrations. On the basis of data for total metal concentrations, 10 topsoil samples were selected to carry out a metal fractionation study using a selective extraction method. A set of four leaches of increasing strength was used sequentially in the soil samples. Across the study area, there is some evidence of past mining and exploration activity, indicating that these soils may be locally disturbed. The shallow mineralised quartz veins were exploited for gold by the Romans. Several galleries were constructed during the 2nd World War, probably for the exploration of quartz–cassiterite–wolframite veins. However, the main mineralised body in depth was never explored. The results of metal fractionation show different partitions for the three elements. Total Cd concentrations in these soils are low, with a median value of 0.1 mg/kg. In average, 12% of total Cd is adsorbed by clays and/or co-precipitated with carbonates, and 19% is bounded to Fe–Mn oxyhydroxides. However, the low concentrations indicate that the metal does not represent an immediate risk to human health. For Pb, metal fractionation shows that, on average, 22% of Pb is adsorbed by amorphous Fe and Mn oxides, but the samples from the northern part of the area have the major fractions of Pb in soluble forms. The low probability of exposure in this part of the study area decreases the risk posed by this heavy metal. Total As concentrations in the Marrancos soils are extremely high. A large area has As concentrations above 1,000 mg/kg. For As, metal fractions in the sulphide phase vary between 84 and 98% in the studied samples. But one sample has 20% of total As in easily reducible forms, corresponding to a partial concentration of 1,800 mg/kg that has a high probability of being bioavailable. The most labile As forms occur at the southern part of the area, where the probability of exposure is higher and the risk of human health increases in the same order. From the three studied potentially harmful elements, As is certainly the element of concern.     

Chemical speciation and bioaccessibility of lead in surface soil and house dust,Lavrion urban area,Attiki, Hellas

In the Lavrion urban area study, Hellas, a five-step sequential extraction method was applied on samples of ‘soil’ (n = 224), affected by long-term mining and metallurgical activities, and house dust (n = 127), for the purpose of studying the potential bioaccessibility of lead and other metals to humans. In this paper, the Pb concentrations in soil and house dust samples are discussed, together with those in rocks and children’s blood. Lead is mainly associated with the carbonate, Fe–Mn oxides and residual fractions in soil and house dust. Considering the very low pH of gastric fluids (1–3), a high amount of metals, present in soil (810–152,000 mg/kg Pb) and house dust (418–18,600 mg/kg Pb), could be potentially bioaccessible. Consequently, children in the neighbourhoods with a large amount of metallurgical processing wastes have high blood-Pb concentrations (5.98–60.49 μg/100 ml; median 17.83 μg/100 ml; n = 235). It is concluded that the Lavrion urban and sub-urban environment is extremely hazardous to human health, and the Hellenic State authorities should urgently tackle this health-related hazard in order to improve the living conditions of local residents.     

Assessing geochemical influence of traffic and other vehicle-related activities on heavy metal contamination in urban soils of Kerman city,using a GIS-based approach

Heavy metal pollution caused by traffic activities is increasingly becoming a great threat to urban environmental quality and human health. In this paper, soils of Kerman urban and suburban areas were collected to assess the potential effects of traffic and other vehicle-related pollution by heavy metal accumulation in soils. Eighty-six samples were collected along streets and from residential and rural sectors, as well as vehicle-related workshops from depth of 0–5 and 15–20 cm and analyzed by flame atomic absorption spectrometry (FAAS) for heavy metals (Cd, Cr, Cu, Pb, Sn and Zn), as well as major elements (Al, Ca, Fe and Mn). Several hot-spot areas were identified in the composite geochemical maps produced based on Geographical Information System (GIS) technology. The majority of the hot-spot areas were identified to be vehicle-related workshops, fuel stations and road junctions. The most polluted hot-spot in the study area was located in soils close to a car battery processing workshop in the southwestern part of Kerman city, with concentrations of Cd (0.32 mg/kg), Cr (169 mg/kg), Cu (250 mg/kg), Pb (5,780 mg/kg), Sn (27.2 mg/kg) and Zn (178 mg/kg) of 1, 8.5, 8.3, 230, 13.5 and 3 times more than the relevant mean concentrations in natural soils, respectively. Traffic pollution has resulted in significant accumulation of heavy metals in soils and sediments, and that level of accumulation varied remarkably among elements. Based on X-ray diffraction analysis, most parts of soils and sediments of the Kerman basement consist of calcite and clay minerals. Abundance of clay minerals and medium to alkaline pH causes low mobility of heavy metals in soils of Kerman.     

Assessment of nutrients and heavy metals enrichment in surface sediments from Taihu Lake,a eutrophic shallow lake in China

Concentrations of the nutrients (TN and TP), phosphorus fractions and heavy metals (Co, Cr, Cu, Mn, Ni, Pb, Sr, Ti, V, Zn and Hg) in 40 surface sediment samples collected from Taihu Lake, a eutrophic shallow lake in China, were determined. The results showed that the northwest region of the lake possessed higher concentrations of TN and TP, as well as the similar spatial distribution trend in the water column. This should be related to excessive anthropogenic input from industrial effluents and domestic sewage in surrounding areas. Similarly, the concentrations of P fractions exhibited significant regularity. In addition, except for Sr showing low concentration, the rest of the heavy metals in the surface sediments had two- to four-folds of magnitude of the concentrations compared with the reference values in earth's crust. In the past decade, concentrations of heavy metals had undergone different levels of variations. Principal component analysis (PCA) and enrichment factors (EFs) of the compositional data aiming at heavy metals showed that Taihu Lake was slightly exposing to heavy metal contamination except Sr. High concentrations of heavy metals were ascribed to the discharge of untreated and partially treated industrial waste water via rivers. Co, Cr, Cu, Mn, Ni, Pb, V and Zn positively correlated with each other (R = 0.78–0.92), that indicated they had analogous sources and/or kindred geochemistry characteristics. Differing from nutrients, randomness in the space indicated that heavy metals had a complex distribution.     

Seasonal AVS–SEM relationship in sediments and potential bioavailability of metals in industrialized estuary, southeastern Brazil

In anoxic sediments, as those found in estuaries, the mobility of metals can be controlled by the formation of stable sulfide complexes. The potential bioavailability of a metal can then be predicted on the basis of the acid volatile sulfide (AVS) and simultaneously extracted metals (SEM) criterion. Distributions of AVS and SEM (Hg, Cu, Pb, Cd, Zn, and Ni) along the sediment profiles were determined seasonally for three rivers that constitute the Santos-Cubat?o estuarine system (SE Brazil), which is located in one of the most industrialized areas of Latin America. AVS and SEM concentrations varied significantly, from 0.04 to 31.9 μmol g⁻¹ and 0.086–6.659 μmol g⁻¹, respectively. The highest AVS levels in sediments were detected in the winter, whereas high SEM values predominated in the summer. Considering SEM–AVS molar differences as a parameter to evaluate potential bioavailability, sediments nearest to the industrial area represent higher risk to biota, especially during the summer. It is due to relatively low AVS values and not necessarily high concentrations of metals.     

Trace Metal Distribution and Enrichment in Benthic, Estuarine Sediments: Southport Broadwater, Australia

The distribution and enrichment of selected trace metals (Cd, Cr, Cu, Ni, Pb, Sn, Zn) in benthic sediments of the Southport Broadwater, a semi-enclosed coastal body of water adjacent to the Gold Coast city, south-eastern Queensland, Australia, was studied with the objective of assessing the extent and degree of sediment contamination. Sediment samples from the 0–10 cm and 10–20 cm depth intervals of 32 sites within the Southport Broadwater and surrounding residential canals were analysed for particle size distribution, pH, organic C and ‘near-total’ major (Al, Ca, Fe, Mn) and trace (Cd, Cr, Cu, Ni, Pb, Sn, Zn) metal contents. Sediment contamination for each trace metal was assessed by (1) comparison with Australian sediment quality guidelines, (2) calculation of the index of geoaccumulation based on regional background values, and (3) geochemical normalisation against Al (i.e. the abundance of alumino-silicate clay minerals). Based on this approach, the results indicate that submerged sediments in the study area are not presently enriched with Cd, Cr or Ni, with the spatial distribution of these metals being very well explained by the abundance of alumino-silicate clay minerals. However, several sites were strongly enriched with Cu, Pb, Sn and Zn, arising from sources related to either urban runoff or vessel maintenance activities. The study indicates that several varying approaches are needed for a satisfactory assessment of contaminant enrichment in estuarine sediments.     

Spatial and temporal characterization of trace elements and nutrients in the Rawal Lake Reservoir,Pakistan using multivariate analysis techniques

Rawal Lake Reservoir is renowned for its ecological significance and is the sole source of drinking water of the third largest city of Pakistan. However, fish kill in recent years and anthropogenic impacts from human-related activities in its catchment area have resulted in deterioration of its surface water quality. This study aims to characterize spatial and temporal variations in surface water quality, identify contaminant sources, and compare their levels with quality guidelines. Surface water samples were collected from 10 sites and analyzed for 27 physicochemical parameters for a period of 2 years on a seasonal basis. Concentration of metals in surface water in pre-monsoon were in the order: Fe > Mg > Ca > Mn > Zn > Ni > Cr > Cu > Co > Pb, whereas in post-monsoon, the order of elemental concentrations was: Ca > Mg > Na > Fe > K > Zn > Cr > Li > Pb > Co > Ni > Cu > Mn > Cd. Metals (Ni, Fe, Zn, and Ca), pH, electrical conductivity (EC), dissolved oxygen (DO), chemical oxygen demand (COD), and nutrients (PO₄³⁻, NO₃–N, and SO₄²⁻) were measured higher in pre-monsoon, whereas concentration of Cu, Mn, Cr, Co, Pb, Cd, K, Na, Mg, Li, Cl⁻, and NH₄–N were recorded higher in post-monsoon. Results highlighted serious metal pollution of surface water. Mean concentration of Zn, Cd, Ni, Cu, Fe, Cr, and Pb in both seasons and Mn in post-monsoon were well above the permissible level of surface water quality criteria. Results stress the dire need to reduce heavy-metal input into the lake basin and suggest that heavy-metal contamination should be considered as an integral part of future planning and management strategies for restoration of water quality of the lake reservoir.     

Particle size distribution and pollutants in road-deposited sediments in different areas of Zhenjiang,China

An understanding of road-deposited sediment (RDS) characteristics on an impervious surface is essential to estimate pollutant washoff characteristics and to minimise the impacts of pollutants on the water environment. A total of 62 RDS samples were collected from four different land-use types (commercial, residential, intense traffic and riverside park) in Zhenjiang City, China. The samples were fractionated into seven grain-size classes and analysed for particle size distribution and concentrations of pollutants. The samples are found to consist predominantly of fine particles (60–80%, <250 μm). The maximum mean concentrations of zinc, lead and copper were 686.93, 589.19 and 158.16 mg/kg, respectively, with the highest metal concentrations found in samples from the intense traffic area. The maximum mean contents of organic matter (12.55%), nitrogen (6.31 mg/g) and phosphorus (5.15 mg/g) were found in samples from the commercial area. The concentrations of heavy metals were highest in the smallest particle size fraction analysed (63 μm). The organic matter and nitrogen content generally increased with decreasing particle sizes in the <500-μm particle size range. The results also revealed that most of the total nitrogen (TN) is attached to the finer sediments and that to effectively reduce TN loads in particulates, treatment facilities must be able to remove the finer particles (down to 125 μm for TN).     

Concentrations of inorganic elements in 20 municipal waters in Sweden before and after treatment – links to human health

The water chemistry of 20 municipal water treatment plants in southern Sweden, representing various bedrock situations, and water qualities, were investigated. Four water samples, raw and treated, were collected from each plant and analyzed by predominantly ICP-OES and ICP-MS at four occasions from June to December, 2001. The concentrations of Ca, Mg, K, Na, HCO₃ and a number of micronutrients, varied considerably in treated waters from the studied plants (ranges; Ca: 9.1–53.7 mg L⁻¹, Mg: 1.4–10.9 mg L⁻¹, K: 1.1–4.8 mg L⁻¹, Na; 5.4–75.6 mg L⁻¹, HCO₃: 27–217 mg L⁻¹). The elimination of Fe and Mn from raw water was efficient in all treatments investigated, giving concentrations in treated waters below the detection limits at some plants. Softening filters gave waters with Ca-concentrations comparable to the softest waters in this study. Adjustment of pH by use of chemicals like lye, soda or lime, modified the consumer water composition significantly, besides raising the pH. It was estimated that drinking water contributed to approximately 2.2–13% of the daily Ca uptake, if the gastrointestinal uptake efficiency from food and water was estimated to be around 50%. The corresponding figures for Mg was 1.0–7% and for F 0–59%. None of the studied elements showed any significant time trends in raw or treated waters during the follow-up period. The concentrations of potentially toxic metals such as Al, Pb and U were low and did not indicate risks for adverse health effects (ranges; Al: 0.5–2.3 μg L⁻¹, Pb: 0–0.3 μg L⁻¹, U: 0.2.5 μg L⁻¹).     

Sorption and bioavailability of arsenic in selected Bangladesh soils

The bioavailability of arsenic (As) in the soil environment is largely governed by its adsorption–desorption reactions with soil constituents. We have investigated the sorption–desorption behaviour of As in four typical Bangladeshi soils subjected to irrigation with As-contaminated groundwater. The total As content of soils (160 samples) from the Laksham district ranged from <0.03 to approximately 43 mg kg⁻¹. Despite the low total soil As content, the concentration of As in the pore water of soils freshly irrigated with As-contaminated groundwater ranged from 0.01 to 0.1 mg l⁻¹. However, when these soils were allowed to dry, the concentration of As released in the pore water decreased to undetectable levels. Remoistening of soils to field moisture over a 10-day period resulted in a significant (up to 0.06 mg l⁻¹) release of As in the pore water of soils containing >10 mg As kg⁻¹ soil, indicating the potential availability of As. In soils containing <5 mg As kg⁻¹, As was not detected in the pore water. A comparison of Bangladeshi soils with strongly weathered long-term As-contaminated soils from Queensland, Australia showed a much greater release of As in water extracts from the Australian soils. However, this was attributed to the much higher loading of As in these Australian soils. The correlation of pore water As with other inorganic ions (P, S) showed a strongly significant (P < 0.001) relationship with P, although there was no significant relationship between As and other inorganic cations, such as Fe and Mn. Batch sorption studies showed an appreciable capacity for both As^V and As^III sorption, with As^V being retained in much greater concentrations than As^III.     

Metal distribution in urban soil around steel industry beside Queen Alia Airport,Jordan

The objective of this study was to assess the extent and severity of metal contamination in urban soil around Queen Alia Airport, Jordan. Thirty-two soil samples were collected around steel manufacturing plants located in the Al-Jiza area, south Jordan, around the Queen Alia Airport. The samples were obtained at two depths, 0–10 and 10–20 cm, and were analyzed by atomic absorption spectrophotometry for lead (Pb), zinc (Zn), cadmium (Cd), iron (Fe), copper (Cu) and chromium (Cr) levels. The physicochemical factors believed to affect the mobility of metals in the soil of the study area were also examined, including pH, electrical conductivity, total organic matter, calcium carbonate (CaCO₃) content and cation exchange capacity. The high concentrations of Pb, Zn and Cd in the soil samples were found to be related to anthropogenic sources, such as the steel manufacturing plants, agriculture and traffic emissions, with the highest concentrations of these metals close to the site of the steel plants; in contrast the concentration of Cr was low in the soil sampled close to the steel plants. The metals were concentrated in the surface soil, and concentrations decreased with increasing depth, reflecting the physical properties of the soil and its alkaline pH. The mineralogical composition of the topsoil, identified by X-ray diffraction, was predominantly quartz, calcite, dolomite and minor minerals, such as gypsum and clay minerals. Metal concentrations were compared using one-way analysis of variance (ANOVA) to compute the statistical significance of the mean. The results of the ANOVA showed significant differences between sites for Pb, Cd and Cu, but no significant differences for the remaining metals tested. Factor analysis revealed that polluted soil occurs predominantly at sites around the steel plants and that there is no significant variation in the characteristics of the unpolluted soil, which are uniform in the study area.     

Examining the coupling of carbon and nitrogen cycles in Appalachian streams: the role of dissolved organic nitrogen

Although regional and global models of nitrogen (N) cycling typically focus on nitrate, dissolved organic nitrogen (DON) is the dominant form of nitrogen export from many watersheds and thus the dominant form of dissolved N in many streams. Our understanding of the processes controlling DON export from temperate forests is poor. In pristine systems, where biological N limitation is common, N contained in recalcitrant organic matter (OM) can dominate watershed N losses. This recalcitrant OM often has moderately constrained carbon:nitrogen (C:N) molar ratios (approximately 25-55) and therefore, greater DON losses should be observed in sites where there is greater total dissolved organic carbon (DOC) loss. In regions where anthropogenic N pollution is high, it has been suggested that increased inorganic N availability can reduce biological demand for organic N and therefore increase watershed DON losses. This would result in a positive correlation between inorganic and organic N concentrations across sites with varying N availability. In four repeated synoptic surveys of stream water chemistry from forested watersheds along an N loading gradient in the southern Appalachians, we found surprisingly little correlation between DON and DOC concentrations. Further, we found that DON concentrations were always significantly correlated with watershed N loading and stream water [NO3-] but that the direction of this relationship was negative in three of the four surveys. The C:N molar ratio of dissolved organic matter (DOM) in streams draining watersheds with high N deposition was very high relative to other freshwaters. This finding, together with results from bioavailability assays in which we directly manipulated C and N availabilities, suggests that heterotrophic demand for labile C can increase as a result of dissolved inorganic N (DIN) loading, and that heterotrophs can preferentially remove N-rich molecules from DOM. These results are inconsistent with the two prevailing hypotheses that dominate interpretations of watershed DON loss. Therefore, we propose a new hypothesis, the indirect carbon control hypothesis, which recognizes that heterotrophic demand for N-rich DOM can keep stream water DON concentrations low when N is not limiting and heterotrophic demand for labile C is high.     

Geochemical and biological controls on trace metal transport in an acid mine impacted watershed

Water samples collected in an acid mine impacted watershed indicated that the concentrations of dissolved trace metals were diurnally influenced by mineral saturation, which is controlled primarily by pH and water temperature. Measurements taken suggested that these variations only occur at sample locations immediately downstream from the confluence of acidic and alkaline waters. It is at these locations where initial mineral precipitation occurred and where subtle changes in solubility were most affected, increasing trace metal removal when both the rate of photosynthesis (influencing pH in headwaters) and water temperature were at a maximum. The role of iron photoreduction (increased midday production of ferrous iron) on overall Cu, Mn, and Zn transport was also evaluated, but found to be inconclusive. Iron photoreduction may however influence adsorption and/or coprecipitation of trace metals through associated changes in oxidation state, solubility, and mineralogy of various iron colloids, which are produced upon the neutralization of acidic, metal enriched water. Furthermore, measured values of copper and zinc were compared to relative USEPA chronic criterion for exposure to continuous concentration (CCC) of metals by the calculation of a “toxicity unit” (TU). It was found that average values of both copper and zinc only exceeded the CCC (TU>1) in the acid mine-impacted Leona Creek. In general, zinc toxicity decreased while copper toxicity increased downstream of the confluence of the mine impacted Leona Creek and background Lion Creek (sampled at Lake Aliso), indicating a significant source of zinc in upstream, non mine-impacted samples.     

Effects of sulphur deposition on trace metal solubility in soils

Concentrations of Fe, Mn, Zn, Pb, Cu and Cd in soil solutions taken in the vicinity of a sulphur mine range from 354 to 9080 μM L⁻¹, and exceeded the concentrations measured in solutions from light acid arable soils. The content of each metal was a negative function of either the solution pH or of Ca concentration. Reclamation of S-contaminated soil by an application of 2000 tonnes of limestone per hectare did not significantly affect the solubility of trace metals, whereas equilibration of soil samples with CaCO₃ in the laboratory decreased solubility of metals, especially in the soil under moist conditions. Sulphur deposition may modify the natural cycling of metals in soils.     

Effect of long-term irrigation with sewage effluent on the metal content of soils, Berlin, Germany

This study aimed to determine whether >110 years of sewage application has led to recognizable changes in the metal chemistry of soils from former sewage farms, Berlin, Germany. Background concentrations of soils and element enrichment factors were used for the evaluation of possible perturbations of natural element abundances in sewage farm soils. Calculations verify that precious metals (Ag, Au) as well as P, C_org, and heavy metals (Cd, Cu, Ni, Pb, Sn, and Zn) are invariably enriched in sewage farm topsoils (0–0.1 m depth) compared to local and regional background soils. Long-term irrigation of soils with municipal wastewater has caused significant heavy metal contamination as well as a pronounced enrichment in precious metals. Leaching of metals including Ag into underlying aquifers may impact on the quality of drinking water supplies.