Transport of trace elements under different seasonal conditions: Effects on the quality of river water in a Mediterranean area

Concentrations of total and dissolved elements were determined in 35 water samples collected from rivers in Sardinia, a Mediterranean island in Italy. The overall composition did not change for waters sampled in both winter and summer (i.e., January at high-flow condition and June at low-flow condition), but the salinity and concentrations of the major ions increased in summer. Concentrations of elements such as Li, B, Mn, Rb, Sr, Mo, Ba and U were higher in summer with only small differences between total and dissolved (i.e., in the fraction <0.4 μm) concentrations. The fact that these elements are mostly dissolved during low flow periods appears to be related to the intensity of water–rock interaction processes that are enhanced when the contribution of rainwater to the rivers is low, that is during low-flow conditions. In contrast, the concentrations of Al and Fe were higher in winter during high flow with total concentrations significantly higher than dissolved concentrations, indicating that the total amount depends on the amount of suspended matter. In waters filtered through 0.015 μm pore-size filters, the concentrations of Al and Fe were much lower than in waters filtered through 0.4 μm pore-size filters, indicating that the dissolved fraction comprises very fine particles or colloids. Also, Co, Ni, Cu, Zn, Cd and Pb were generally higher in waters collected during the high-flow condition, with much lower concentrations in 0.015 μm pore-size filtered waters; this suggests aqueous transport via adsorption onto very fine particles. The rare earth elements (REE) and Th dissolved in the river waters display a wide range in concentrations (∑REE: 0.1–23 μg/L; Th: <0.005–0.58 μg/L). Higher REE and Th concentrations occurred at high flow. The positive correlation between ∑REE and Fe suggests that the REE are associated with very fine particles (>0.015 and <0.4 μm); the abundance of these particles in the river controls the partitioning of REE between solution and solid phases.Twenty percent of the water samples had dissolved Pb and total Hg concentrations that exceeded the Italian guidelines for drinking water (>10 μg/L Pb and >1 μg/L Hg). The highest concentrations of these heavy metals were observed at high-flow conditions and they were likely due to the weathering of mine wastes and to uncontrolled urban wastes discharged into the rivers.     

Monitoring and modelling of the solid-solution partitioning of metals and As in a river floodplain redox sequence

For a period of 2 a, pore water composition in a heavily contaminated river floodplain soil was monitored in situ. Pore water samples were collected 12 times over all seasons in a profile ranging from aerobic to sulphidic redox conditions, and As, Cd, Cr, Cu, Pb, Zn, Mn, Fe, Ca, Cl, SO₄, DOC, IOC and pH were determined. The variability of pH, IOC, DOC and Ca was found to be rather small during the year and within the profile (rsd < 0.04, 0.16, 0.24 and 0.22, respectively). The temporal variability of the metal and As concentrations was small, too, whereas changes with depth were distinct. Under sulphidic conditions, concentrations were below 1 μg L⁻¹ (Cd, Cu, Pb) or 10 μg L⁻¹ (Zn, As). The data set was compared with results from a geochemical model that was fully parameterised from literature data and included equilibrium speciation, sorption and mineral dissolution. The general pattern of the solid–solution partitioning of Cd, Cu, Zn and As in the profile was predicted well by mechanistic geochemical modelling on the basis of solid phase composition. Metals strongly bound to organic matter such as Cd and Cu were predicted better than metals mainly present within a mineral. Detailed information regarding the presence of colloidal Fe and Mn in pore water might improve the prediction of the solid–solution partitioning of a number of metals. The study also indicates that the chemical behaviour of Pb is still not understood sufficiently.     

A preliminary study on the enrichment mechanism and occurrence of hazardous trace elements in the Tertiary lignite from the Shenbei coalfield, China

The Cr and Ni contents are high in the Eocene lignite of the Shenbei coalfield, which is a small intracontinental basin located in Liaoning Province, China. In this paper, we studied the distribution, origin and occurrence of Cr, Ni and other hazardous trace elements in the Shenbei lignite on the basis of coal petrology, and geochemistry of the lignite and combustion products. The following conclusions on the Shenbei lignite can be drawn: (1) The dominant maceral group in the Shenbei coal is huminite (humodetrinite), accounting for 96%–99% of the total maceral. Inertinite content is less than 1%. Liptinite content (sporinite and cutinite) is 0.2–1.6%. Common minerals in the Shenbei lignite include clay minerals (kaolinite), pyrite and quartz, and calcite and siderite. Chromite is not present in the lignite. (2) Potentially hazardous trace elements such as Co (22 μg/g), Cr (79 μg/g), Cu (63 μg/g), Zn (93 μg/g), V (88 μg/g) and Ni (75 μg/g) are strongly enriched in the Shenbei lignite compared with average concentration of trace elements in the Chinese coal and worldwide lignite. These elements are mainly associated with fulvic acid (FA) and/or coal organic macromolecular compounds in most of the studied lignite samples, indicating an organic association and enrichment of these elements in the Shenbei lignite. (3) Unusually high trace elements contents in the Shenbei lignite are derived mainly from the olivine basalt (country rock of coal basin) that consists of 52.7% plagioclase, 17.8% pyroxene, 14% olivine and 15.5% Ti–Fe oxide minerals. These olivine basalts have higher Cr, Ni, Pb and Zn contents than other types of rock and worldwide basalts do. (4) Fly ash of the Shenbei lignite, with 90% 1–50 μm amorphous particles and 8% 1–10 μm cenosphere, has high contents of Zn (23,707 μg/g), Be (12 μg/g), Sr (1574 μg/g), Pb (486 μg/g) and Cr (349 μg/g). In particular, the ferruginous micro-cenoshperes contain 1–12.79% Zn. Fine bottom ash (<0.031mm) of the Shenbei lignite has higher contents for most of the elements with the exception of Mo, Sn and Zn. Therefore, the potentially environmental and health impact of the fly ash and fine bottom ash should constitute a major concern.     

Lignin is preserved in the fine silt fraction of an arable Luvisol

Knowledge about the fate of individual biomolecules during the decomposition process in soil is limited. We used the natural isotopic label introduced by 23 years of continuous maize cropping, together with compound specific ¹³C isotope analysis, to study lignin monomers in particle size fractions of a Luvisol. Isotope data indicated apparent decadal turnover times for lignin. A kinetic model suggests the existence of a fast and a slow decomposing lignin pool in the soil, reconciling a low stock-to-input ratio with decadal turnover times. We found new, maize-derived lignin primarily in the 63–2000 μm fraction, whereas old, C₃-derived lignin from the pre-maize vegetation had accumulated mainly in the silt (2–20 μm) fraction. This distribution of lignin differed from that of total organic carbon, which was concentrated in the <2 μm fraction. Old, C₃-derived carbon in all the soil fractions was depleted in lignin compared to new, maize-derived carbon. The observation that the 2–20 μm fraction was less depleted than the others indicates that lignin preservation is particle size specific, but the underlying mechanism controlling its preservation is not clear.     

Distribution of copper, zinc, lead and cadmium concentrations in stream sediments from the Mapocho River in Santiago, Chile

The Mapocho river, which crosses downtown Santiago, is one of the most important rivers in contact with a population of about six million inhabitants. Anthropogenic activities, industrialization, farming activities, transport, urbanization, animal and human excretions, domestic wastes and copper mining have affected the river, contaminating it and its sediments with heavy metals. Concentration and distribution of Cu, Zn, Pb and Cd were studied with the purpose of determining their bioavailability and their relation with the characteristics of the sediments. Freshly deposited seasonal sediments were collected from 0–8 cm depths from 6 locations (S₁ to S₆) along the 30-km long channel length, in the four seasons of year on the following dates: May 2001 (D₁, autumn); August 2001 (D₂, winter); October 2001 (D₃, spring) and January 2002 (D₄, summer). The dried samples were sifted to obtain the < 63-μm sediment fraction, since it has been shown that large amounts of heavy metals are bound in the fine-grained fraction of the sediment. Cu and Zn were analyzed by atomic absorption spectrophotometry and Pb and Cd by square wave anodic stripping voltammetry. The highest concentrations of Cu (2850 μg g^− 1) were found in the northern part of the river (S₁, average D₁–D₄), near the mountains and a copper mine, and then decreased downstream to 209 μg g^− 1 (S₆). Total Zn showed an irregular variation, with higher values at S₁ (1290 μg g^− 1) and high values in some winter sampling (1384 μg g^− 1 S₄, S₅–D₂). Pb showed different trends, increasing from S₁ to S₆ (17 to 61 μg g^− 1), with the highest values in the summer samples (83 μg g^− 1, S₄–S₆, D₄), and total Cd increased slightly from mean values of 0.2 and 0.5 μg g^− 1. Partition into five fractions was made using Tessier's analytical sequential extraction technique; the residue was treated with aqua regia for recovery studies, although this step is not part of the Tessier procedure. The results show that Cu, Zn and Pb in the sediments were dependent on the sampling places along the river, and variation in two years was low (D₁–D₄). The highest values of total organic matter, carbonate and conductivity were found in S₆, which has the smallest size particles, while at S₁ the sediments were predominantly sand and contain larger amounts of silica. Cu associated with carbonate decreased gradually from 58% (1771 μg g^− 1, S₁) to 16% (32 μg g^− 1, S₆); Cu bonded to reducible fraction was almost constant (33% to 37%), and Cu associated with oxidizable fraction increased from 7% (S₁) to 34% (S₆), but copper content was lower (214 to 68 μg g^− 1). Zn had a similar fractionation profile. However, Pb bound to oxidizable fraction did not show significant percent variation along the river (20% to 19%), but the amount bounded was 4 to 12 μg g^− 1. The residual fraction increased from 24% to 41% (5 to 25 μg g^− 1, S₁ to S₆). The distribution of Cd in the sediment was almost independent of the sampling stations and was bound to carbonate, reducible and residual fraction in similar proportion. Cu and Zn at S₁ were mainly bound to carbonates and reducible phases with 91% and 73% (2779 and 965 μg g^− 1, respectively), and with a change in the pH and/or the redox potential of the sediment–water system, these contaminants could easily enter the food chain. In S₆ the amount of Cu and Zn in these phases was 50% and 53% (100 to 313 μg g^− 1, respectively).     

Contamination,bioaccessibility and human health risk of heavy metals in exposed-lawn soils from 28 urban parks in southern China's largest city,Guangzhou

The total concentrations and oral bioaccessibility of heavy metals in surface-exposed lawn soils from 28 urban parks in Guangzhou were investigated, and the health risks posed to humans were evaluated. The descending order of total heavy metal concentrations was Fe > Mn > Pb > Zn > Cu > Cr > Ni > Cd, but Cd showed the highest percentage bioaccessibility (75.96%). Principal component analysis showed that Grouped Cd, Pb, Cr, Ni, Cu and Zn, and grouped Cr and Mn could be controlled two different types of human sources. Whereas, Ni and Fe were controlled by both anthropogenic and natural sources. The carcinogenic risk probabilities for Pb and Cr to children and adults were under the acceptable level (<1 × 10⁻⁴). Hazard Quotient value for each metal and Hazard Index values for all metals studied indicated no significant risk of non-carcinogenic effects to children and adults in Guangzhou urban park soils.     

Geological controls on soil parent material geochemistry along a northern Manitoba–North Dakota transect

As a pilot study for mapping the geochemistry of North American soils, samples were collected along two continental transects extending east–west from Virginia to California, and north–south from northern Manitoba to the US–Mexican border and subjected to geochemical and mineralogical analyses. For the northern Manitoba–North Dakota segment of the north–south transect, X-ray diffraction analysis and bivariate relations indicate that geochemical properties of soil parent materials may be interpreted in terms of minerals derived from Shield and clastic sedimentary bedrock, and carbonate sedimentary bedrock terranes. The elements Cu, Zn, Ni, Cr and Ti occur primarily in silicate minerals decomposed by aqua regia, likely phyllosilicates, that preferentially concentrate in clay-sized fractions; Cr and Ti also occur in minerals decomposed only by stronger acid. Physical glacial processes affecting the distribution and concentration of carbonate minerals are significant controls on the variation of trace metal background concentrations.     

Distribution of Cd,Pb, Zn and Cu and their chemical speciations in soils from a peri-smelter area in northeast China

An exploratory study on soil contamination of heavy metals was carried out surrounding Huludao zinc smelter in Liaoning province, China. The distribution of total heavy metals and their chemical speciations were investigated. The correlations between heavy metal speciations and soil pH values in corresponding sites were also analyzed. In general, Cd, Zn, Pb, Cu and As presented a significant contamination in the area near the smelter, comparied with Environmental Quality Standards for Soils in China. The geoaccumulation index showed the degree of contamination: Cd > Zn > Pb > Cu > As. There was no obvious pollution of Cr and Ni in the studied area. The speciation analysis showed that the dominant fraction of Cd and Zn was the acid soluble fraction, and the second was the residual fraction. Pb was mostly associated with the residual fraction, which constituted more than 50% of total concentration in all samples. Cu in residual fraction accounted for a high percentage (40–80%) of total concentration, and the proportion of Cu in the oxidizable fraction is higher than that of other metals. The distribution pattern of Pb and Zn was obviously affected by soil pH. It seemed that Pb and Zn content in acid solution fraction increased with increasing soil pH values, while Cd content in acid soluble fraction accounted for more proportion in neutral and alkaline groups than acidic one. The fraction distribution patterns of Cu in three pH groups were very similar and independent of soil pH values. And the residual fraction of Cu took a predominant part (50%) of the total content.     

Chemistry of rainwaters in the south Pacific area of Russia

On the south-eastern edge of Russia, the chemical composition of rainwater is controlled by sea salts, terrestrial material, as well as volcanic (Kuril islands volcanic area) and anthropogenic emissions, mostly in the southern part of the area. The predominant major ions of the Primorye, Sakhalin and the Kuril Islands rainwaters were respectively HCO₃⁻–SO₄²⁻, Ca–Na, and of Cl–Na. Concentration of trace elements changes within 1–2 orders of magnitude but some difference in the distribution of the elements between continental and island rainwater is found. The concentration of the chemical elements in the particulate fraction varies from < 10% to 90% of the total concentration (dissolved + particulate) with the following distribution: Tl, Na, Ca, Sr, Zn, Cd (< 10%)–Be, Th, Bi, Rb, U, K, Sc (10–20%)–Cu, Mn, Mg, Mo, Se, Ba, Ni, As, Ag, Cs, Co, Y, Ga, V (20–50%)–Sb, Pb, Ge, Cr, Fe, Al (50–90%).The concentration of elements of the particulate fraction of the rainwater usually is significantly different from concentrations in the crust, including both higher and lower concentrations. The terrestrial contribution to dissolved elements was evaluated and follows the decreasing order: Fe > K, Mg, Ca > Ba, Sr > Na (65–1%). Close order was found for total (dissolved and solid) concentrations. Sea salt contribution to dissolved element concentration in the rainwater decrease in the following order: Cl, Mg > K, SO₄ > Ca > HCO₃⁻, Ba, Fe (78–0.1%). Calculation of anthropogenic and volcanic inputs for two ions (Cl⁻ and SO₄²⁻) shows that anthropogenic inputs for the Vladivostok and Yuzno-Sakhalinsk cities can be evaluated as 15–20% of Cl⁻ and up to 80–90% of SO₄²⁻. Volcanic components in the Kuril Islands, where anthropogenic inputs are absent, can reach up to 76% of SO₄²⁻ and 36% of Cl⁻.     

A regional-scale study of chromium and nickel in soils of northern California, USA

A soil geochemical survey was conducted in a 27,000-km² study area of northern California that includes the Sierra Nevada Mountains, the Sacramento Valley, and the northern Coast Range. The results show that soil geochemistry in the Sacramento Valley is controlled primarily by the transport and weathering of parent material from the Coast Range to the west and the Sierra Nevada to the east. Chemically and mineralogically distinctive ultramafic (UM) rocks (e.g. serpentinite) outcrop extensively in the Coast Range and Sierra Nevada. These rocks and the soils derived from them have elevated concentrations of Cr and Ni. Surface soil samples derived from UM rocks of the Sierra Nevada and Coast Range contain 1700–10,000 mg/kg Cr and 1300–3900 mg/kg Ni. Valley soils west of the Sacramento River contain 80–1420 mg/kg Cr and 65–224 mg/kg Ni, reflecting significant contributions from UM sources in the Coast Range. Valley soils on the east side contain 30–370 mg/kg Cr and 16–110 mg/kg Ni. Lower Cr and Ni concentrations on the east side of the valley are the result of greater dilution by granitic sources of the Sierra Nevada.Chromium occurs naturally in the Cr(III) and Cr(VI) oxidation states. Trivalent Cr is a non-toxic micronutrient, but Cr(VI) is a highly soluble toxin and carcinogen. X-ray diffraction and scanning electron microscopy of soils with an UM parent show Cr primarily occurs within chromite and other mixed-composition spinels (Al, Mg, Fe, Cr). Chromite contains Cr(III) and is highly refractory with respect to weathering. Comparison of a 4-acid digestion (HNO₃, HCl, HF, HClO₄), which only partially dissolves chromite, and total digestion by lithium metaborate (LiBO₃) fusion, indicates a lower proportion of chromite-bound Cr in valley soils relative to UM source soils. Groundwater on the west side of the Sacramento Valley has particularly high concentrations of dissolved Cr ranging up to 50 μg L⁻¹ and averaging 16.4 μg L⁻¹. This suggests redistribution of Cr during weathering and oxidation of Cr(III)-bearing minerals. It is concluded that regional-scale transport and weathering of ultramafic-derived constituents have resulted in enrichment of Cr and Ni in the Sacramento Valley and a partial change in the residence of Cr.     

K–Ar dating of fault gouge in the northern Sydney Basin, NSW, Australia—implications for the breakup of Gondwana

The occurrence of synkinematic and authigenic clay minerals is a common feature in fault gouges. Few attempts have been made to date fault gouges. We present the first age data in Australia for synkinematic illite–smectite growth in two fault zones of the northern Sydney Basin, NSW. The faults occur at Burwood Beach, NSW in the northern part of the Sydney Basin and are hosted by Early Permian siltstones, tuffs and coals of the Lambton Formation, Newcastle Coal Measures. The faults are 1.5 m apart, show normal displacement and trend N–S with steep easterly dips. Foliated gouge zones, comminution and dilational breccias are developed along both fault surfaces. K–Ar ages extracted from samples in the gouge and tuffs in the damage zones are 172 (6–10 μm) to 119 Ma (<0.4 μm), respectively. Older ages of 272–281 Ma for the coarse fractions (>2 μm), 237–245 Ma for the <2 μm fraction, 218 Ma for the <0.4 μm fraction and 196 Ma for the <0.1 μm fraction have been obtained from siltstones within and outside the damage zone. We believe the younger ages of 196–237 Ma indicate the time at which diagenetic illite–smectite formed and the 122–150 Ma dates from the <2 μm fraction represent the maximum age of gouge formation. The younger ages are thought to reflect the last slip event occurring on the faults, which is related to the rifting and dispersal of the eastern margin of the Australian continent.     

The influence of physicochemical parameters on bioavailability and bioaccessibility of heavy metals in sediments of the intertidal zone of Asaluyeh region,Persian Gulf,Iran

In this research, we have worked on the evaluation of heavy metal contamination in the sediments taken from the intertidal zone of Asaluyeh region using Modified Community Bureau of Reference sequential extraction method (mBCR), the simplified bioaccessibility extraction test (SBET), and calculated enrichment factor (EF). Also, potential influencing factors including sediment characteristics that may affect the heavy metals bioavailability and bioaccessibility were investigated. mBCR extraction analysis indicated that among the metals, Mn, Zn, V, Cu, and Cd exhibit relatively higher mobility, while Ti, Pb, Cr, and Ni occur mainly in the residual fractions. Based on the mean values, the bioaccessibility of metals decreased in the order: Mn (50.01%)>Cd (46.26%)>Zn (14.61%)>V (13.97%)>Pb (10.88%)>Ni (9.2%)>Ti (8.43%)>Cr (6.66%)>Cu (6.23%). The obtained results from the principal component analysis (PCA), EF and mBCR extraction showed that most anthropogenic-derived metals with higher solubility are more bioaccessible compared to those of natural origin. Multiple linear regression analysis demonstrated that the main physicochemical variables of the sediment influencing the bioaccessibility of metals include cation exchange capacity (CEC), pH, and particle size fraction.     

Quantitative spatial characteristics and environmental risk of toxic heavy metals in urban dusts of Shanghai,China

Associated with the rapid urbanization and industrialization, most of the urban parks and recreational areas in Shanghai are built close to major roads or industrial areas, where they are subject to many potential pollution source, including automobile exhaust and factory emissions. Urban dusts, containing many toxic heavy metals such as Pb, Cr, Cd, Hg and As, are one of main contributors for environmental pollution. In this study, 261 dust samples were collected from two different localities (streets and parks) in the urban area of Shanghai, China. Pb and Cr concentrations of all samples were determined by atomic adsorption spectrophotometer analyzer, and Cd, As and Hg concentrations in 74 samples by atomic fluorescence spectroscopy. The mean concentrations of Pb, Cr, Cd, As and Hg are 287, 157, 1.24, 8.73 and 0.16 mg kg⁻¹, respectively. Each heavy metal shows a wide range of concentration values. In comparison with heavy metal background values of soil in Shanghai, urban dusts have elevated metal concentrations as a whole, except those of As. The concentrations of Pb, Cr, Cd, As and Hg are 11.3, 2.1, 10.3, 0.997, 1.7 times of the soil background values, respectively. Compared with the global mean concentrations, Cr concentration in urban dusts is slightly higher. Pb, Cr and Hg show normal distribution after logarithmic transformation. Pb, Cr, Cd, As and Hg have second-order variation trends of the spatial distribution. The spatial distribution features of five toxic heavy metals, in general, illustrate relatively high levels within the regions of the inner-city ring highway and southwestern Shanghai. Cr and Cd are higher in Baoshan industrial park and the shipbuilding industries regions. The order of environmental risk is Pb > Cd > Cr > Hg > As. Pb and Cd have the highest risk for environment pollution and human health among the five metals. The pollutant sources of toxic heavy metals in Shanghai urban dusts are preliminarily concluded as follows: As may have mainly a natural source. Burning of coal has become the main source of Hg pollution. Pb, Cr and Cd have three sources, traffic, building construction, and weathering corrosion of building materials.     

Heavy metals pollution in the soil of an irregular urban settlement built on a former dumpsite in the city of Tijuana, Mexico

The aim of this study was to evaluate soil pollution by heavy metals in an irregular settlement built on a dumpsite. The soil samples were analyzed for Cd, Cr, Cu, Pb and Ni. None of the concentrations found for the heavy metals analyzed were higher than the established Mexican official standards for contaminated soils. The mean concentrations found for the analyzed metals were as follows: 1.4 mg kg⁻¹ for Cd, 4.7 in mg kg⁻¹ for Cr, 304 mg kg⁻¹ for Cu, 74 mg kg⁻¹ for Pb and 6 mg kg⁻¹ for Ni. The results of the geoacummulation index values show that the site was very polluted with Cu and Pb (class 7), polluted to strongly polluted with Ni (class 4); moderately polluted to polluted with Cd (class 3), and moderately polluted with Cr (class 1). The correlation analysis shows a high correlation between Pb and Cu (r ² = 0.98), which would be explained if the main source of the polluting heavy metals was the result of electrical wire burning to recover Copper. Principal component analysis shows three principal components. The first main component (PC1) encompasses Cr, Cd, Pb and Cu. These heavy metals most likely have their origins from the open burning of municipal solid waste, tires and wire. The other two components are encompassed by Cr (PC2) and Ni (PC3). The sources of these pollutants are more likely related to the corrosion of junk metal objects and automobile use.     

A water-leach procedure for estimating bioaccessibility of elements in soils from transects across the United States and Canada

An objective of the North American Soil Geochemical Landscapes Project is to provide relevant data concerning bioaccessible concentrations of elements in soil to government and other institutions undertaking environmental studies. A protocol was developed that employs a 1-g soil sample agitated overnight with 40 mL of reverse-osmosis de-ionized water for 20 h, and determination of 63 elements following three steps of centrifugation by inductively coupled plasma–atomic emission spectrometry and inductively coupled plasma–mass spectrometry the following day. Statistical summaries are presented for those 48 elements (Ag, Al, As, B, Ba, Be, Br, Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga, Gd, Ge, Hf, Ho, I, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, Nd, Ni, P, Pb, Pr, Rb, Re, S, Sb, Si, Sm, Sn, Sr, Tb, Ti, Tl, Tm, U, V, W, Y, Yb, Zn, Zr, and pH) for which <20% of their data were reported as below the detection limit. The resulting data set contains analyses for 161 A-horizon soils collected along two transects, one along the 38th parallel across the USA and the other from northern Manitoba to the USA–Mexico border. The spatial distribution of three selected elements (Ca, Cu, and Pb) along the two transects is discussed in this paper both as absolute amounts liberated by the leach and expressed as a percentage of the total, or near-total, amounts determined for the elements. The Ca data reflect broad trends in soil parent materials, their weathering, and subsequent soil development. Calcium concentrations are generally found to be lower in the older soils of the eastern USA. The Cu data are higher in the eastern half of the USA, correlating with soil organic C, with which it is sequestered. The Pb data exhibit little regional variability due to natural sources, but are influenced by anthropogenic sources. Based on the Pb results, the percentage water-extractable data demonstrate promise as a tool for identifying anthropogenic components. The soil–water partition (distribution) coefficients, K_ds (L/kg), were determined and their relevance to estimating bioaccessible amounts of elements to soil fauna and flora is discussed. Finally, a possible link between W concentrations in human urine and water-extractable W levels in Nevada soils is discussed.     

Field trial using bone meal amendments to remediate mine waste derived soil contaminated with zinc, lead and cadmium

Bone meal amendments are being considered as a remediation method for metal-contaminated wastes. In various forms (biogenic, geogenic or synthetic), apatite, the principal mineral constituent of bone, has shown promise as an amendment to remediate metal-contaminated soils via the formation of insoluble phosphates of Pb and possibly other metals. The efficacy of commercially available bovine bone meal in this role was investigated in a field trial at Nenthead, Cumbria with a mine waste derived soil contaminated with Zn, Pb and Cd. Two 5 m² plots were set up; the first as a control and the second, a treatment plot where the soil was thoroughly mixed with bone meal to a depth of 50 cm at a soil to amendment ratio of 25:1 by weight. An array of soil solution samplers (Rhizon SMS^™) were installed in both plots and the soil pore water was collected and analysed for Ca, Cd, Zn and Pb regularly over a period of 2 a. Concurrently with the field trial, a laboratory trial with 800 mm high and 100 mm wide leaching columns was conducted using identical samplers and with soil from the field site.A substantial release of Zn, Pb, Cd and Ca was observed associated with the bone meal treatment. This release was transient in the case of the leaching columns, and showed seasonal variation in the case of the field trial. It is proposed that this effect resulted from metal complexation with organic acids released during breakdown of the bone meal organic fraction and was facilitated by the relatively high soil pH of 7.6–8.0. Even after this transient release effect had subsided or when incinerated bone meal was substituted in order to eliminate the organic fraction, no detectable decrease in dissolved metals was observed and no P was detected in solution, in contrast with an earlier small column laboratory study. It is concluded that due to the relative insolubility of apatite at above-neutral pH, the rate of supply of phosphate to soil solution was insufficient to result in significant precipitation of metal phosphates and that this may limit the effectiveness of the method to more acidic soils.     

Lithogenic concentrations of trace metals in soils and saprolites over crystalline basement rocks: A case study from SW Nigeria

In this study, an assessment of the lithogenic concentrations of trace metals in soils and saprolite over basement rock units in Ibadan, SW-Nigeria is presented in respect of bedrock types and geochemical controls on the weathering-associated release of trace metals. Consequently, soil, weathered and fresh rock samples from the Precambrian Basement of SW Nigeria were collected from three different bedrock units within Ibadan metropolis and subjected to mineralogical and geochemical analyses. The analytical results revealed major proportions of oxides in the range of 18–20% Al₂O₃, 2–6% Na₂O and 1–6% K₂O for weathered profiles over granite-gneiss and pegmatite units, compared to 2–3% Al₂O₃, <0.5% Na₂O and <1.0% K₂O over schist-quartzite. For the trace elements, weathered profiles on granite-gneiss and schist-quartzite settings exhibit similar enrichment trends (enrichment factor, EF l) for most of the trace elements, unlike the pegmatite bedrock. However, enrichments are relatively greater in the top soil unit compared to the intermediate saprolite unit, especially for Pb, Ni, Zn, Cr, Co, Rb, Sr and Ba, a situation attributed to leaching and redistribution within the weathered profiles through pedogenetic process and percolating groundwater.Furthermore, the estimated weathering indices using Ruxton Ratio (RR = {SiO₂/Al₂O₃}) and Chemical Index of Alteration (CIA = 100{Al₂O₃/[Al₂O₃ + CaO + Na₂O + K₂O]}) revealed RR of 2.9–3.7 and CIA of 54–73% for granite-gneiss and pegmatite units, implying medium levels of weathering, compared to RR of 30.8–35.5 and CIA of >60% for schist-quartzite units, which suggest weak chemical weathering. Also, the estimated high percentage loss, especially for Pb, Rb, Sr, Ba relative to the bedrocks, shows that the trace elements can be mobilized within the weathering profiles even at a low degree of chemical weathering. Such weathering-induced release of trace metals is of environmental significance as natural lithogenic input sources and as background reference for future monitoring of possible human/anthropogenic impacts.     

Distribution and immobilization of heavy metals in Pliocene aquifer sediments in Wadi El Natrun depression, Western Desert

The Pliocene aquifer receives inflow of Miocene and Pleistocene aquifer waters in Wadi El Natrun depression. The aquifer also receives inflow from the agricultural activity and septic tanks. Nine sediment samples were collected from the Pliocene aquifer in Wadi E1 Natrun. Heavy metal (Cu, Sr, Zn, Mn, Fe, Al, Ba, Cr, Ni, V, Cd, Co, Mo, and Pb) concentrations of Pliocene aquifer sediments were investigated in bulk, sand, and mud fractions. The determination of extractable trace metals (Cu, Zn, Fe, Mn, and Pb) in Pliocene aquifer sediments using sequential extraction procedure (four steps) has been performed in order to study environmental pathways (e.g., mobility of metals, bounding states). These employ a series of successively stronger chemical leaching reagents which nominally target the different compositional fractions. By analyzing the liquid leachates and the residual solid components, it is possible to determine not only the type and concentration of metals retained in each phase but also their potential ecological significance. Cu, Sr, Zn, Mn, Fe, and Al concentrations are higher in finer sediments than in coarser sediments, while Ba, Cr, Ni, V, Cd, Co, Mo, and Pb are enriched in the coarser fraction. The differences in relative concentrations are attributed to intense anthropogenic inputs from different sources. Heavy metal concentrations are higher than global average concentrations in sandstone, USEPA guidelines, and other local and international aquifer sediments. The order of trace elements in the bulk Pliocene aquifer sediments, from high to low concentrations, is Fe?>?Al?>?Mn?>?Cr?>?Zn?>?Cu?>?Ni?>?V?>?Sr?>?Ba?>?Pb?>?Mo?>?Cd?>?Co. The Pliocene aquifer sediments are highly contaminated for most toxic metals, except Pb and Co which have moderate contamination. The active soluble (F0) and exchangeable (F1) phases are represented by high concentrations of Cu, Zn, Fe, and Mn and relatively higher concentrations of Pb and Cd. This may be due to the increase of silt and clay fractions (mud) in sediments, which act as an adsorbent, retaining metals through ion exchange and other processes. The order of mobility of heavy metals in this phase is found to be Pb?>?Cd?>?Zn?>?Cu?>?Fe?>?Mn. The values of the active phase of most heavy metals are relatively high, indicating that Pliocene sediments are potentially a major sink for heavy metals characterized by high mobility and bioavailability. Fe–Mn oxyhydroxide phase is the most important fraction among labile fractions and represents 22% for Cd, 20% for Fe, 11% for Zn, 8% for Cu, 5% for Pb, and 3% for Mn. The organic matter-bound fraction contains 80% of Mn, 72% of Cu, 68% of Zn, 60% of Fe, 35% of Pb, and 30% of Cd (as mean). Summarizing the sequential extraction, a very good immobilization of the heavy metals by the organic matter-bound fraction is followed by the carbonate-exchangeable-bound fraction. The mobility of the Cd metal in the active and Fe–Mn oxyhydroxide phases is the highest, while the Mn metal had the lowest mobility.     

Chromium and nickel distribution in soils, active river, overbank sediments and dust around the Burrel chromium smelter (Albania)

Chromium ore was treated to produce ferrochromium from 1979 until 2000 in a smelter in Burrel, 35 km NE of Tirana (Albania). As a consequence, large amounts of solid waste, i.e. slags (about 9.10⁶ m³) have been disposed next to the smelter, disfiguring the landscape. In an attempt to define contaminated sites, heavy metal content of the different sampling media have been compared with respective background samples.In the study area, the determination of background values in soil samples is complicated due to the different geological substrates. Cr and Ni background concentrations in serpentinite-derived soils, west of the smelting plant, are markedly higher than in the Pliocene gravel/sandy soils, where the smelter is situated (Cr 2147 and 193 mg/kg, respectively; Ni 2356 and 264 mg/kg). These values are clearly lower than those encountered around the smelter. Average total Cr and Ni concentrations in soils around the smelter are 3117 and 1243 mg/kg, respectively. The highest concentrations of Cr (up to 2.3 wt.%), were recorded in samples taken near the smelting compartment within the industrial plant and next to the slags clearly indicating that the smelter forms a point source of Cr contamination. The Cr / Fe ratio is the best indicator to differentiate non-polluted (Cr / Fe Serpentinite soil: 130–390; Pliocene soils: < 130) from polluted areas (> 390 smelting nearby of the slags).Cr and Ni values for local backgrounds in stream and overbank sediments were taken in the Mat river 6 km upstream and to the east of the smelter (268 and 430 mg/kg for Cr, and 306 and 604 mg/kg for Ni, respectively). Equivalent sediments taken from the Zalli i Germanit river, which drains the smelter area are respectively 816 and 1126 mg/kg for Cr and 1115 and 1185 mg/kg for Ni.Dust samples, taken from the lofts of houses up to 2 km from the smelter, display high concentrations of Cr, Ni and Zn (average contents of 2899, 436 and 902 mg/kg, respectively). The later concentrations in the dust samples have been confirmed by mineralogical analysis where Cr-bearing mineral phases such as ferrochromium and chromium oxides, clearly relate to the activity of the smelter. Consequently, atmospheric deposition of dust particles forms a serious problem and can also be responsible for the elevated contents encountered in soil samples around the smelter.All these data show that the degree of contamination caused by industrial activity of the Burrel Cr-smelter is severe, although no Cr(VI) was detected in soil water extractions nor in the surface or groundwater where concentrations were < 0.01 mg/kg.     

Lead in archaeological samples: an isotopic study by ICP-MS

Inductively coupled plasma mass spectrometry (ICP-MS) has been used to measure the concentration and isotopic composition of Pb in archaeological human and animal skeletal remains, soil from a village site of the Omaha tribe (U.S.A.) and cosmetic pigments.Lead concentrations in human bones from the Omaha tribe vary between 4.8 and 2570 μg/g, with younger people having the highest concentrations. Lead concentrations in animal bones from an Omaha village vary between 0.6 and 3.7 μg/g, and those of three soil samples range between 18 and 21 μg/g. Lead concentrations found in human bones from Anasazi (Utah, U.S.A.) and Alta (Peru) populations vary between 0.7 and 3.2 μg/g.Isotope ratios of a reagent grade Pb(NO₃)₂ solutions were measured by thermal ionization mass spectrometry (TIMS), as well as by ICP-MS to provide laboratory reference materials. The accuracy of the ICP-MS measurements relative to TIMS for the standard solution were found to be within 0.02–0.31% for²⁰⁶Pb/²⁰⁴Pb, 0.02–0.55% for²⁰⁷Pb/²⁰⁴Pb, and 0.16–0.56% for²⁰⁸Pb/²⁰⁴Pb. The precision of measurements on artifacts was 0.42–0.65% for²⁰⁶Pb/²⁰⁴Pb and 0.41–0.62% for²⁰⁷Pb/²⁰⁴Pb, whereas the precision for the same ratios for the bones was 0.85–1.8 and 0.82–1.67%, respectively. For the cosmetic lead-bearing pigments, a precision of 0.07–0.15% was found for both²⁰⁶Pb/²⁰⁴Pb and²⁰⁷Pb/²⁰⁴Pb ratios. Lead isotope ratios of artifacts give a radiogenic Pb signature, of which are close to signatures from PbZn mines of the central U.S. region. Lead isotope ratios of the pigments give non-radiogenic Pb signatures. Lead isotope ratios of the bones differ from those of the artifacts, and although similar in isotopic ratio to the pigments, they are more scattered, suggesting potential mixing of Pb from different regions.