Trace elements in surface soils from the mineralized area of Madison County, Missouri, U.S.A.

Duplicate, bulked surface soil samples, from sites 10m apart, were collected at 97 locations 1000 m apart on a regular grid measuring 8x11 km. Data were obtained for Ag, Ba, Be, Cd, Co, Cr, Cu, Li, Mn, Ni, Pb, V and Zn. One field sample was a good predictor of its nearby duplicate for Co, Cu, Ni and Pb, satisfactory for Ba, Be, Cr, Mn and Zn, but poorer for Cr, Li and V. Maps of the variation in precision of the field samples did not reveal any association between abandoned mine sites and high variability. The median coefficient of variation for trace elements in the field duplicates was between 8 and 19.5%. The duplicated field data were averaged to yield a mean soil metal concentration at each sample location. Concentrations of Ba, Be, Cr, Li, Sr and V were comparable with other published values for similar soils in Missouri. Concentrations of Co, Cu, Mn, Ni, Pb and Zn were higher which was explained by pollution from mining activities. A graphical technique was used to calculate background levels for metals in the second group. Samples of forest litter were collected at 12 locations: Ag, Ba, Cd, Mn, Sr and Zn concentrations were higher in the litter whereas Li and V concentrations were higher in the subjacent mineral soil. Computer isoline maps of the distribution of elements revealed an association between areas of high soil Cu, Co, Ni, Pb and Zn and abandoned mines or mineralized rocks.     

Pedogenesis and surface charge of some Andic soils in Washington,U.S.A.

Chemical and surface charge characteristics were determined for three soils that were formed in a mantle of volcanic tephra along a bio-climatic gradient in forest in northcentral Washington state. The soils are Nevine silt loam (Typic Vitrandept), Manley silt loam (Entic Cryandept), and Moses silt loam (Andic Cryochrept). Selective dissolution analyses for Al, Fe, and Si suggests that the weathering products in the ash mantle are poorly crystalline aluminosilicates, hydrous and crystalline Fe-oxides, and Al-humus complexes in decreasing order of abundance. The chemical and physical data indicate that Moses silt loam has undergone a greater degree of weathering than either Nevine silt loam or Manley silt loam, and we attribute this to differences in the weathering environment. The measured points of zero charge parameters are typical for soils that are dominated by amphoteric surfaces: the soils exhibit charge reversal, and charge magnitude is dependent upon pH and electrolyte concentration. The point of zero salt effect ranged from 5.1 to 5.3, and the point of zero net charge ranged from 4.3 in Nevine silt loam to 5.4 in Moses silt loam. Pedogenesis has not caused large enough differentiation among the soils to allow us to use zero charge parameters as indicators of the degree of pedogenesis.     

Anomalous contents of heavy metals in soils and vegetation of a mine area in S.W. Sardinia,Italy

Samples of soils and vegetation from the mining area of South-West Sardinia (Italy) were analyzed for Pb, Zn, Cd, and Cu content. The area (more than 100 km²) is inhabited by many thousands of people; land utilization includes mainly grapes on some small plains and permanent sheep pasture on the hills. The levels of Pb, Zn, and Cd were found to be exceptionally high in most samples. Lead concentration was up to 71000 μg g^?1 in the soils and 4000 jig g^?1 in vegetation; Cd concentration was found up to 665 μg g^?1 in soils and 26.5 μg g^?1 in vegetation. The heavy metal content of some soil samples was highly variable. Data show that Pb is easily absorbed by plant roots and translocated to foliage. In spite of the high heavy metal level, no signs of toxicity were apparent in vegetation.     

Biotreatment and Chemical Speciation of Lead and Zinc Mine/Mill Wastewater Discharges in Missouri,U.S.A.

Continued mining development in the world's largest lead producing area has generated and increased concern over effective mine water treatment in Missouri's New Lead Belt. A new type of mine/mill wastewater treatment system was constructed which consisted of a tailings pond followed by a series of artificially constructed meandering biotreatment channels and a polishing lagoon. This system provided additional retention time and distance for the removal of heavy metals by abundant aquatic plants and sedimentation. Seasonal field sampling and analytical testing that evaluated the present system confirmed that it provided good treatment for removal of heavy metals within the company property and produced a final effluent within the state and federal regulatory guidelines. On average, greater than 95% of zinc and manganese in the drainage water were removed by the biotreatment system, while lead and copper were 50 to 60%. A chemical equilibrium model, MINTEQ, was also used to identify various species of lead and zinc in the biotreatment system. The model predicted that the major species of carbonates and hydroxides would be the predominant complexes of lead and zinc for the pH and alkalinity values reported in the biotreatment system. These results were also supported by the literature.     

Relations between stratigraphy,geomorphology and soils in Coastal Plain areas of Southeastern U.S.A.

Small infiltrometers were used to measure infiltration rates into strongly and maderately developed compound prisms, sampled individually from surface layers of two dry clay soils. Initially, both rates were equally high but after three hours a higher rate was measured for the moderately developed compound prisms. These data were used to interpret adsorption and outflow phenomena of water in undisturbed, large and initially dry soil cores (diameter 20 cm) sampled from the upper 20 cm of the two soils, following application rates of about 8 mm/h and 28 mm/h. The two soils adsorbed an average of 6.4 mm water before the start of discharge, independent of the applied intensity. They discharged water at a constant and high rate for several hours, allowing adsorption of about 10% of the applied water. This represents a high degree of “short-circuiting” for all treatments, except one: adsorption was 40% at the 28 mm/h rate for the soil with the moderately developed prisms. The moisture content in the transmission zone was not constant as it would have been in homogeneous soil but increased regularly as a function of time. Slow wetting of both soils through a crust, followed by rain with an intensity of 30 mm/h, resulted in the adsorption of only about 3% of the applied rain in both soils.In general, more effective wetting of a dry clay surface soil at a given rainfall intensity is initially associated with less “short-circuiting” to deeper horizons. However, the resulting higher moisture content allows less adsorption in the surface layer and is therefore associated with increased “short-circuiting” thereafter, as long as large vertical pores have not been closed by swelling.     

Use of grain-size and elemental normalization in the interpretation of trace metal concentrations in soils of the reclaimed area adjoining Port Jackson, Sydney, Australia

Cobalt, Cr, Cu, Fe, Mn, Ni, Pb, Zn and As concentrations in the grain size and elemental normalization using Fe in gravel-free total soil ((X_m/Fe)_{total sample}; X_m = Cu, Pb, Zn, etc.) were used to determine the influence of variable grain size on the concentration of anthropogenic trace metal contaminants in the reclaimed area adjacent to Port Jackson, Sydney, Australia. Trace metal concentrations in soils in reclaimed area are greatly influenced by the heterogeneous nature of the waste materials buried at the site. The confounding effects of variable grain size in soils can be reduced by analyzing the contaminant concentration of the material after removing > 2 mm size in sample. An example from Sydney Harbour is used to demonstrate the comparability between grain size normalized data and elemental normalized data using Fe in soils from reclaimed areas. Results from the current study reveal that the vertical distribution of trace metal concentrations in soils is remarkably similar between the grain size and elemental normalization, using Fe. Normalization methods might be beneficial in overcoming texturally driven variations of contaminant concentrations in soils in the reclaimed or infilled land area.     

Land use and management of soils with relict duripans,southwestern oregon (U.S.A.)

Paleosolic features are important to land use and management of soils on fan terraces in southwestern Oregon. Soil-geomorphology studies identified relict duripans and established the distribution of associated Durochrepts, Duraquolls and Argixerolls. These soils represent two late Pleistocene geomorphic surfaces, each with distinct kinds of periglacial patterned ground. Soil behavior is discussed in terms of soil characteristics and qualities and compared for cropland, grazing, construction, and waste disposal.     

The origin and early genesis of clay bands in youthful sandy soils along lake Michigan,U.S.A.

A beach ridge and dune complex with good radiocarbon control sampling the last 3500 radiocarbon years B.P. provides new insights on the early genesis of clay bands in sandy soils. Soil profiles were sampled by age groups, described in the field, and then subjected to laboratory analyses for particle-size distribution, pH, organic carbon, carbonate minerals, and extractable iron and manganese. This study suggests that small increases in pH, brought about by small increases in carbonate content within the soil profile, are responsible for flocculating small amounts of illuviated clay. This process, along with a transition to a greater hydraulic conductivity with soil depth due to coarser textures in any given profile, partly explains the existence and possible reason for the initiation of illuvial zones and eventually for clay-band horizons. A pronounced increase in the thickness of incipient clay-band horizons in soils older than 2300 years appears due to finer textures in the parent materials than are present in younger soils. Because of slightly reduced porosity and lower permeability, carbonates and a high pH are retained in both illuvial and eluvial horizons of some of these older soils. In addition, only in those profiles older than 2300 years do clay and iron oxide concentrations coincide and is there some suggestion of greater amounts of extractable manganese in horizons of minimum iron and clay. A pronounced segregation of clay-iron bands is not apparent at the study area but should occur in future years as additional amounts of iron and clay are deposited.     

Baseline element concentrations in soils and plants,Bull Island,Cape Romain National Wildlife Refuge,South Carolina,U.S.A.

Baseline element concentrations are given for Spanish moss (Tillandsia usneoides), loblolly pine (Pinus taeda), and associated soils. Baseline and variability data for ash, Al, Ba, C, Ca, Cd, Ce, Co, Cr, Cu, Fe, K, La, Li, Mg, Mn, Na, Nb, Nd, Ni, P, Pb, S, Sc, Sr, Th, Ti, V, Y, and Zn are reported; however, not all variables are reported for all media because, in some media, certain elements were below the analytical detection limit. Spatial variation in element concentration among and within 0.5 km grid cells are given for each of the media. In general, only a few elements in Spanish moss showed statistically significant landscape patterns, whereas several elements in loblolly pine and in soils exhibited differences among sampling grids. Significant differences in the concentration of three elements in Spanish moss and eight elements (including total S) in loblolly pine were observed between two sampling dates (November and June); however, the absolute amount of these differences was small. Except for perhaps Ni and Pb concentrations in Spanish moss, element levels in all sample media exhibited ranges that indicate natural rather than anthropogenic additions of trace elements.     

Heavy metals in European soils: A geostatistical analysis of the FOREGS Geochemical database

This paper presents the results of modeling the distribution of eight critical heavy metals (arsenic, cadmium, chromium, copper, mercury, nickel, lead and zinc) in topsoils using 1588 georeferenced samples from the Forum of European Geological Surveys Geochemical database (26 European countries). The concentrations were mapped using regression-kriging (RK) and accuracy of predictions evaluated using the leave-one-out cross validation method. A large number of auxiliary raster maps (topographic indexes, land cover, geology, vegetation indexes, night lights images and earth quake magnitudes) were used to improve the predictions. These were first converted to 36 principal components and then used to explain spatial distribution of heavy metals. The study revealed that this database is suitable for geostatistical analyses: the predictors explained from 21% (Cr) to 35% (Pb) of variability; the residuals showed spatial autocorrelation. The Principal Component Analysis of the mapped heavy metals revealed that the administrative units (NUTS level3) with highest overall concentrations are: (1) Liege (Arrondissement) (BE), Attiki (GR), Darlington (UK), Coventry (UK), Sunderland (UK), Kozani (GR), Grevena (GR), Hartlepool & Stockton (UK), Huy (BE), Aachen (DE) (As, Cd, Hg and Pb) and (2) central Greece and Liguria region in Italy (Cr, Cu and Ni). The evaluation of the mapping accuracy showed that the RK models for As, Ni and Pb can be considered satisfactory (prediction accuracy 45-52% of total variance), marginally satisfactory for Cr, Cu, Hg and Zn (36-41%), while the model for Cd is unsatisfactorily accurate (30%). The critical elements limiting the mapping accuracy are: (a) the problem of sporadic high values (hot-spots); and (b) relatively coarse resolution of the input maps. Automation of the geostatistical mapping and use of auxiliary spatial layers opens a possibility to develop mapping systems that can automatically update outputs by including new field observations and higher quality auxiliary maps. This approach also demonstrates the benefits of organizing standardized joint European monitoring projects, in comparison to the merging of several national monitoring projects.     

Predicted acid mine drainage impacts to the Buckhannon River,WV, U.S.A.

This study was conducted to determine acid, Al, Cd, Cu, Fe, Mn, and Zn loads originating from coal mines in the Buckhannon River watershed in central West Virginia, U.S.A, and to predict the impacts of those loads should they enter the river as unneutralized acid mine drainage. Net alkaline loads at the river mouth would decrease from 3341 to 1014 and 7488 to 1463 kg day^?1 CaCO₃ during the summer and spring sampling periods, respectively, causing pH decrease below the level required for surviveal of warm water fish species in the affected study area and for a viable trout fishery in a 12 km segment of the river. Aluminum could have major impacts through much of the study area. Zinc could impact the existing cold water fishery and may cause deleterious effects to the warm water fishery. It was not possible to draw accurate conclusions about impacts of Fe because of the uncertainties of toxicity data and rates of oxidation. It appears that Cd and Cu would probably not impact the river. Manganese may cause a water treatment problem for the city of Buckhannon.     

Soil-geomorphology relations in mountains of Oregon,U.S.A.

The development and distribution of soils in the Coast Range and Klamath Mountains are related to geomorphic surfaces and slope gradients. Soils over basalt, studied in the Coast Range, were formed in transported materials and include examples of more than a half dozen great groups of the Alfisol, Inceptisol, Mollisol, and Ultisol orders. Distribution patterns of the soils can be related to active slopes, metastable slopes, pediments, ridge tops, flood plains, and alluvial fans. Variables among the factors of soil formation in the Coast Range are chiefly geomorphic surfaces and parent materials.Soils of a lithosequence of pyroclastics, granite and schist in the Klamath Mountains include examples of great groups in the Entisol, Inceptisol, and Mollisol orders. All soils from pyroclastics have argillic horizons, those from granite lack argillic horizons, and those from schist lack argillic horizons except on relatively stable surfaces. Average thicknesses of soils over saprolite range from 76 cm over granite and schist to 150 cm over pyroclastics.Lithologic discontinuities are common in both mountain areas. Field techniques for identification, described briefly, include stone lines, irregular distribution of rock fragments with depth, thicknesses of weathering rinds on rock fragments, and the lateral extensions of soil horizons.     

Metal concentrations in muscle of fish from aquatic systems in east Tennessee,U.S.A.

Heavy metal residues (i.e., As, Cd, Cu, Pb, Mn, Hg, and Zn) were determined in striated muscle of 268 fish specimens harvested during a 5-yr period (1980–1984) from several aquatic systems in east Tennessee (U.S.A.). Elevated concentrations of Hg, Mn, and Cd were found in the muscle of fish from several of the aquatic systems studied; concentrations of Hg exceeded the U.S. Food and Drug Administration action level of 1.0 ppm for food intended for human consumption. In general, the concentrations of the other metals in fish muscle were low. Moreover, muscle metal content did not vary among the three fish groups (i.e., game fish, catfish, and rough fish) investigated at any one of the nine sampling stations established. The results of this study are in agreement with the 1978–1979 pilot survey of Young and Blevins (1981) conducted at the same sampling stations. It appears that, in this region of Tennessee, heavy metal contamination of fish tissues has neither improved nor deteriorated during the last 5 yr.     

洞庭湖地区红土微量与稀土元素地球化学特征及其环境意义

Trace element (TE) and rare earth element (REE) contents in red soils from the Dongting Lake area of China were determined to understanding the provenance and weathering characteristics of the red soils. The results showed similar REE distribution patterns among red soils from the Dongting Lake area, Xiashu loess from Zhenjiang, loess and the Pliocene red soil from the Loess Plateau. These patterns implied a similar provenance from dust-storms, except for red soil R5 which formed by bedrock weathering and had significant light REE (LREE) enrichment and heavy REE (HREE) depletion due to longer weathering periods and higher intensity of weathering. Trace element, especially the Rb/Sr and Li/Ba ratios, and REE, especially the LREE/HREE ratio and δEu could trace weathering intensity. Higher Rb/Sr, Li/Ba, and LREE/ HREE ratios and negative Eu anomalies were present in the red soil from the Dongting Lake area. The weathering intensity was in the decreasing order of R5 in the Dongting Lake area > red soil from the Dongting Lake area (including reticulate red soil, weak reticulate red soil, and homogeneous red soil formed by dust storms) > Xiashu loess from Zhenjiang > Loess-paleosol and Pliocene red soil from the Loess Plateau. Variations in the TE and REE contents of soil could be effectively used to study the provenance and the weathering intensity.     

Evaluation and source identification of trace element contamination of soils in the Qixia lead-zinc mining area,Jiangsu, China

Purpose

The Qixia mine is one of the largest lead-zinc mines in Eastern China and has been operational for approximately 60 years. Source identification for trace element contamination of soils in the Qixia mining area has been lacking. This report details the evaluation and source identification of trace element contamination (including Cu, Zn, Pb, Cd, Hg, Cr, As, and Ni) of soils in this area.

Materials and methods

Thirty-three soil samples from roadsides and fields in the study area were collected and analyzed. The index of geo-accumulation (I _geo) was employed to evaluate contamination. Methods of multivariate statistical analysis were used to determine the probable sources of the pollutants.

Results and discussion

The analysis showed that the levels of contamination ranked in the following order: Cd > Pb/Zn> > As/Cu> > Hg > Cr/Ni. In the sampling area nearest the mine, soil samples collected from roadsides showed much higher levels of contamination than those collected from fields away from the roadways. Trace element contamination decreased as the distance from the mine increased. Contamination extended to a distance of approximately 700 m from mineral transportation routes, with the area of greatest impact at 200 m or less. Multivariate statistical analysis and ore composition data suggest that the Cu, Zn, Pb, Cd, and As found in the soil samples originate from anthropogenic sources. Ni and Cr are considered to be at natural background concentrations.

Conclusions

This study distinguished between natural and anthropogenic sources of trace element contamination in the soils of the Qixia mining area. The contamination of Cu, Zn, Pb, Cd, and As is linked to the mining activities and is likely due to the transportation of ore concentrates and tailings.     

Failure of spring turnover in Onondaga Lake,NY, U.S.A.

Onondaga Lake, N.Y., failed to turnover in the spring of 1986 because of the strong chemical stratification under the ice that developed as a result of ionic discharges from an alkali plant. This stratification had a negative impact on the O₂ resources of the lake, as the lower depleted layers of the lake were not replenished with O₂. Anoxia and anaerobiesis in the bottom water expanded following ‘ice-out’. Comparison of characteristics observed for the winter through spring interval of 1986 with historic data indicates Onandaga Lake has failed to experience spring turnover in a number of years (approximately 7 of the last 18 yr) because of the ionic discharges from the alkali plant.     

Metal concentrations in the ground water of the Ouachita Mountains,Arkansas, U.S.A.

Ninety-one ground water samples (predominantly from springs) in two mineralized areas of the Ouachita Mountains in west-central Arkansas, were analyzed for Fe, Mn, Zn, Cu, Co, Ni, Pb, Hg, Sb, Sr, Ba, Ca, and Li. These areas contain Mn, barite, strontianite, cinnabar, stibnite and scattered Pb-Zn mineralization, Cumulative frequency curves were used to determine the threshold and anomalous concentrations for each element in the two areas. These values were, in general, higher in the ground water from the more mineralized area for several of the base metals, but most notably for Mn and Fe, the principal metals in the Mn oxide minerals. The United States Environmental Protection Agency (EPA, 1976) criteria for Fe (300 μg L ^?1) and Mn (50 μg L^?1) in drinking water were exceeded, respectively, in 34% and 30% of the springs in Area I, and 13% and 23% in Area II. One spring exceeded the EPA Hg criterion (2 μg L^?1) and 3 springs exceeded the 50 μg L^?1 criterion for Pb. In spite of the large number of anomalous Ba concentrations, the highest concentration of Ba was 930 μg L^?1 (EPA criterion 1000 μg L ^?1).     

The role of organic acids in the acidification of surface waters in the Eastern U.S.

There is considerable uncertainty concerning the role of naturally occurring organic solutes in the acidification of surface waters. To provide a preliminary assessment of this process, we evaluated water chemistry data obtained from the US EPA Eastern Lake Survey (ELS). A wide range of dissolved organic carbon (DOC) and organic anion concentrations were evident across acid-sensitive lake districts in the Eastern US. In particular, lakes in Maine, the Upper Midwest and Florida contained high concentrations (greater than 1000 gmol C · L^?1) of DOC. High concentrations of organic anions, estimated by discrepancy in charge balance in several subregions, suggest that dissociation of naturally occurring organic acids could significantly reduce the ANC of dilute surface waters. Unfortunately, analysis of acidification by organic solutes is complicated by uncertainty in H⁺ dissociation characteristics. Input of organic acids with weakly acidic pK _a values do not alter acid neutralizing capacity (ANC), while strongly acidic organic functional groups dissociate completely and decrease ANC. As a first step to assess the acid/base characteristics of naturally occurring organic solutes, we calibrated the Oliver et al. (1983) model, using a reduced version of the ELS data set. This model explained 94% of the observed variability in organic anion concentration in this data set. However, model parameters obtained from the ELS calibration were somewhat different than values provided by Oliver et al. (1983), based on potentiometric titrations of pre-concentrated organic acids. The discrepancy in model parameters has implications for estimating organic anion concentrations in water using the Oliver et al. (1983) model. Finally, data from the ELS indicates that across glaciated regions of the eastern US, concentrations of DOC and organic ions were negatively correlated with SO _inf2? ^p4 . This trend would appear to be consistent with the hypothesis that inputs of strong acids immobilize organic acids, resulting in a shift of surface water acidification by organic acids to strong acids.     

A re-examination of closed flux chamber methods for the measurement of trace gas emissions from soils to the atmosphere

The most widely used method for measuring the emission of a trace gas such as N₂O from soil to the atmosphere involves the accumulation of the gas under closed chambers followed by sampling and analysis (by gas chromatography or infrared methods). These chambers can affect the gas exchange, and so improved designs have been proposed. We have tested their performance. One design includes a vent tube to allow ambient pressure fluctuations to occur also inside the chamber. We tested it against a sealed version on two different grassland sites during N₂O peak emissions in spring 1997. On a welldrained soil with a fairly large air permeability vented chambers yielded fluxes as much as five times those of sealed chambers, depending on wind speed. By contrast, on a heavier and wetter soil with smaller air permeability vented chambers averaged only 88% of the fluxes observed with sealed chambers. The effects of venting cannot be explained solely on the basis of mean pressure differences inside and outside the chamber. It seems more likely that wind blowing over the vent depressurizes the chamber (Venturi effect), resulting in significant gas flow from the more permeable soil into the interior of the chamber. The opposite trend for the less permeable soil suggests that diffusion losses through the vent tube are greater than the increase in concentration due to soil gas flow. Venting can create larger errors than the ones it is supposed to overcome.