Competitive Effect of Copper,Zinc, Cadmium and Nickel on Ion Adsorption and Desorption by Soil Clays

This study evaluated the effect of competing copper, zinc, cadmium and nickel ions in 0.01 M Ca(NO₃)₂ on heavy metal sorption and desorption by soil clay fractions. Initial Cu addition levels varied from 99 mg kg^-1 to 900 mg kg^-1 and Zn, Cd and Ni levels were 94, 131 and 99 mg kg^-1, respectively. Sorption of Cu conformed to a Freundlich equation. The amounts of metals not displaced by successive 48 h desorption cycles with 0.01 M Ca(NO₃)₂ were considered ‘specifically adsorbed’. Total sorption of Zn and Cd generally decreased in the order: Vertisol > Gleyic Acrisol > Planosol clay. More than 70% of the copper was specifically sorbed. Specific sorption of Zn was depressed by competition with Cu in the three clays investigated. At surface coverages higher than 200 mg Cu per kg of soil clay, zinc sorption in the Planosol and Gleyic Acrisol clays took place at low affinity sites. The exchangeable component of sorbed cadmium accounted for >:60% of the sorption in the Vertisol clay, >70% in the Gleyic Acrisol clay and was almost 100% in the Planosol clay. Nickel was not retained by the Planosol and Gleyic Acrisol clays and was ionexchangeably adsorbed by the Vertisol clay. At the conditions studied, Ni and Cd remain a ready source of pollution hazard.     

Competitive Removal of Heavy Metals from Aqueous Solutions by Montmorillonitic and Calcareous Clays

A batch sorption method was used to study the removal of few toxic metals onto the Late Cretaceous clays of Aleg formation (Coniacian–Lower Campanian system), Tunisia, in single, binary and multi-component systems. The collected clay samples were used as adsorbents for the removal of Pb(II), Cd(II), Cu(II) and Zn(II) from aqueous solutions. Results show that the natural clay samples were mainly composed of silica, alumina, iron and magnesium oxides. N₂-adsorption measurements indicated mesoporous materials with modest specific surface area of <71 m²/g. Carbonate minerals were the most influencing parameters for heavy metal removal by natural clays in both single and multi-element systems. The affinity sequence was Pb(II)>Cu(II)>Zn(II)>Cd(II) due to the variable physical properties of the studied metals. The maximum adsorption capacity reached 131.58 mg/g in single systems, but decreased to <50.10 mg/g in mixed systems. In single, binary and muti-element systems, the studied clay samples removed substantial amounts of heavy metals, showing better effectiveness than the relevant previous studies. These results suggest that the studied clay samples of the Late Cretaceous clays from Tunisia can be effectively used as natural adsorbents for the removal of toxic heavy metals in aqueous systems.     

The sorption of Cd,Zn and Ni by soil clay fractions: Procedures for partition of bound forms and their interpretation

This work is the first of several projects concerned with the study of higher-affinity reactions of Cd, Zn and Ni ions with soil clay fractions. Procedures for the separation of sorbed metals into fractions of lower and higher affinity for soil surfaces are described and evaluated.Various concentrations of Cd, Zn and Ni were allowed to react in the presence of 0.01 M Ca(NO₃)₂ with soil clays for 1 week after stabilization of suspension pH. The adsorbed metals were partitioned by a brief extraction with 0.01 M Ca(NO₃)₂ and the resultant fractions, called specifically and non-specifically sorbed metals, were measured by radioisotopic procedures.Measured separation factors showed that the fraction of sorbed metals that was desorbed by a rapid Ca(NO₃)₂ extraction still had a preference, sometimes marked, over Ca on the soil clay fraction. Separation of fractions of sorbed metals on the basis of affinity was reproducible, but the boundary conditions defined by separation factors vary appreciably between adsorbents, with values in the range 3–20 for amounts sorbed equivalent to ≦ 0.05% of cation exchange capacity and for pH values < 7.The proportions of Cd, Zn and Ni bound at high-affinity sites were strongly dependent on experimental conditions of pH, equilibrium time and surface saturation in relation to each soil clay. Hence, comparisons of affinities of trace metals for soils by reliance on measures of total sorption only, without assessing the contribution of lower-affinity forms, may prejudice conclusions and predictions arising from studies of the possible retention of metal pollutants in soils and fixation of micronutrients from fertilizers.     

华中黄棕壤和黄褐土粘粒胶膜的微量元素地球化学特征

The relationships between the basic properties and trace elementsin soil argillans and corresponding matrix soils were studied by sampling from the B horizons of 26 Alfisols in croplands of the subtropical area in Central China. The soil elements (K, Na, Ca, Mg, Mn, Co, Cu, Cr, Cd, Li, Mo, Ni, Pb, Ti, V, and Zn) were extracted by acid digestion and their contents were measured using inductively coupled plasma optical emission spectrometry (ICP-OES). The mean contents of clay and organic matter in the argillans were approximately 1.1 and 1.3 times greater than those in the matrix soils, respectively. The pH values and the contents of P₂O₅ and bases (K₂O, Na₂O, CaO, and MgO) in the argillans were higher than those in the corresponding matrix soils. Cu, Cd, Ti, and V were enriched in the argillans. Correlation coefficients and factor analyses showed that Co, Cu, Li, and Zn were bound with phyllosilicates and manganese oxides (Mn-oxides) in the argillans. Cr and Pb were mainly associated with iron oxides (Fe-oxides), while Ni was bound with Mn-oxides. Cd, Ti, and V were chiefly associated with phyllosilicates, but Cr and Mo were rarely enriched in the argillans. In contrast, in the matrix soils, Co and Zn were associated with organic matter and Fe-oxides, Cr existed in phyllosilicates, and Mo was bound to Fe-oxides. Cd, Ti, and V were associated with organic matter. The results of this study suggest that clays, organic matter, and minerals in the argillans dominate the illuviation of trace elements in Alfisols. Argillans might be the active interfaces of elemental exchange and nutrient supply in cropland soils in Central China.     

Zinc sorption–desorption by sand,silt and clay fractions in calcareous soils of Iran

Zinc sorption–desorption by sand, silt and clay fractions of six representative calcareous soils of Iran were measured. Sand, silt and clay particles were fractionated after dispersion of soils with an ultrasonic probe. Zinc sorption analysis was performed by adding eight rates of Zn from 6 to 120 μmol g^?1. For the desorption experiment, samples retained after the measurement of Zn sorption were resuspended sequentially in 0.01 M NaNO₃ solution and shaken for 24 h. Results indicated that Zn sorption by soil fractions increased in the order clay > silt > sand, and correlated negatively with CaCO₃ content and positively with cation exchange capacity (CEC) and smectite content. Results indicated that for all fractions, the Langmuir equation described the sorption rates fairly well. In contrast to sorption, Zn desorption from soil fractions increased in the order sand > silt > clay, and correlated positively with CaCO₃ content, CEC and smectite content. Results showed that parabolic diffusion and two constant equations adequately described the reaction rates of Zn desorption. In general, for all soils studied, the coarser the particle size, the less Zn sorption and more Zn desorption, and this reflects much higher risk of Zn leaching into groundwater or plant uptake in contaminated soils.     

Differential Sorption Behavior of Cadmium,Lead, Zinc,and Copper in Some Tropical Soils and Their Environmental Implications

This study evaluated cadmium (Cd), lead (Pb), zinc (Zn), and copper (Cu) sorption characteristics of three tropical soils. Data obtained conformed to Freundlich sorption model and the S-shaped isotherm curve. Sorption efficiency of Zn and Pb were highest in alkaline soil while slightly acid soil had the highest Cd and Cu sorption efficiency for monometal sorption. In competitive sorption, metals were more sorbed in slightly acid soil while the least efficiency was recorded in acid soil. Distribution coefficient; K_d (average across soil types) in monometal sorption followed the order: Pb > Zn > Cd > Cu. For competitive sorption, the order was Zn > Pb > Cu > Cd. When in competition, Cd was preferentially sorbed in slightly acid and alkaline soils and Zn for acid soil. Conclusively, lead is more in equilibrium solution when in competition with Cd, Zn and Cu making it potential agent of soil and groundwater pollution.     

The transfer of heavy metals to barley plants from soils amended with sewage sludge with different heavy metal burdens

Purpose

Our main aim objective was to evaluate the transfer of Cd, Cr, Cu, Ni, Pb and Zn to barley (Hordeum vulgare) grown in various soils previously amended with two sewage sludges containing different concentrations of heavy metals. This allowed us to examine the transfer of heavv metals to barley roots and shoots and the occurrence of restriction mechanisms as function of soil type and for different heavy metal concentration scenarios.

Material and methods

A greenhouse experiment was performed to evaluate the transfer of heavy metals to barley grown in 36 agricultural soils from different parts of Spain previously amended with a single dose (equivalent to 50 t dry weight ha^?1) of two sewage sludges with contrasting levels of heavy metals (common and spiked sludge: CS and SS).

Results and discussion

In soils amended with CS, heavy metals were transferred to roots in the order (mean values of the bio-concentration ratio in roots, BCF_Roots, in brackets): Cu (2.4)?~?Ni (2.3)?>?Cd (2.1)?>?Zn (1.8)?>?Cr (0.7)?~?Pb (0.6); similar values were found for the soils amended with SS. The mean values of the soil-to-shoot ratio were: Cd (0.44)?~?Zn (0.39)?~?Cu (0.39)?>?Cr (0.20)?>?Ni (0.09)?>?Pb (0.01) for CS-amended soils; Zn (0.24)?>?Cu (0.15)?~?Cd (0.14)?>?Ni (0.05)?~?Cr (0.03)?>?Pb (0.006) for SS-amended soils. Heavy metals were transferred from roots to shoots in the following order (mean values of the ratio concentration of heavy metals in shoots to roots in brackets): Cr (0.33)?>?Zn (0.24)?~?Cd (0.22)?>?Cu (0.19)?>?Ni (0.04)?>?Pb (0.02) for CS-amended soils; Zn (0.14)?>?Cd (0.09)?~?Cu (0.08)?>?Cr (0.05)?>?Ni (0.02)?~?Pb (0.010) for SS-amended soils.

Conclusions

Soils weakly restricted the mobility of heavy metals to roots, plant physiology restricted the transfer of heavy metals from roots to shoots, observing further restriction at high heavy metal loadings, and the transfer of Cd, Cu and Zn from soils to shoots was greater than for Cr, Ni and Pb. Stepwise multiple linear regressions revealed that soils with high sand content allowed greater soil-plant transfer of Cr, Cu, Pb and Zn. For Cd and Ni, soils with low pH and soil organic C, respectively, posed the highest risk.     

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

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

Role of soil constituents in fixation of soluble Zn, Cu, Ni and Cd added to soils

Slow immobilization of trace metals in soil, termed ‘fixation’, affects their natural attenuation but it is still unclear which reactions occur. Twenty‐eight soils were selected to assess the role of Fe oxides and carbonates on fixation of Cu, Cd, Zn and Ni. Soils included samples from 2 toposequences (Vietnam, Spain) and 13 European topsoils with different soil characteristics (pH 3.4–7.7). Samples were amended with 250 mg Zn kg⁻¹, 100 mg Cu kg⁻¹, 80 mg Ni kg⁻¹ and 2.5 mg Cd kg⁻¹ as metal salts and incubated for 850 days. Fixation was measured as the increase of the fraction of added metals that were not isotopically exchangeable. Fixation increased with time and was, averaged over all the soils, 43% (Cu), 41% (Zn), 41% (Ni) and 28% (Cd) after 850 days. Metal fixation within samples from each toposequence was generally positively related to total Fe oxide concentration (Fe_d) for Zn, Ni and Cd. However, the fixation of Cd, Zn and Ni was mainly explained by pH and not by Fe_d when considering all soils. Fixation of Zn and Cd in soils with pH >7.0 increased with increasing concentrations of carbonates at initial ageing times. Fixed fractions of Zn, Ni and Cd were significantly released when experimentally removing 50% of carbonates by acidification. Fixation of Cu was most poorly related to soil properties. Our data suggest that fixation of Cd, Zn and Ni is related to a pH‐dependent diffusion into oxides and that of Cd and Zn also to diffusion and/or coprecipitation in carbonates. Fixation of Ni at neutral pH may also be related to stabilization of precipitates that form readily in soil.     

新乡市寺庄顶污灌区土壤中重金属的形态分布及生物有效性研究

对长期电池废水灌溉的新乡市寺庄顶污灌区和对照区土壤重金属进行取样分析,结果表明,对照区土壤中Cd,Ni,Zn,Cu和Cr含量都能达标,污灌区土壤中Cr含量能达标,Cd,Ni,Zn和Cu的含量超标,其平均含量分别为65.31,1 196.64,2 799.25,145.78 mg/kg,是国家土壤环境质量二级标准的108.85,19.94,9.33和1.46倍。形态分析结果表明,污灌区污染最严重的Cd主要以铁-锰氧化物结合态存在,所占比例平均为56.84%;Ni主要以铁-锰氧化物结合态和残余态存在,所占比例平均为37.44%和39.55%;Zn主要以残余态存在,所占比例平均为78.24%;Cu主要以有机结合态存在,所占比例平均为57.70%;Cr主要以有机结合态和残余态存在,所占比例平均为45.55%和34.18%。与对照相比,污灌降低了Cd,Ni,Zn,Cu和Cr残余态所占比例,提高了重金属迁移能力和生物有效性。在4种超标重金属中Cd可交换态所占比例最高,平均为24.54%,由于其生物有效性最高,Cd迁移能力和植物毒性最值得关注。     

Distribution of Trace Elements in Soils from the Sudbury Smelting Area (Ontario,Canada)

The sequential extraction procedure proposed by the European Commission Measurement and Testing Programme, combined with Scanning Electron Microscopy and Energy Dispersive X-ray Analysis(SEM/EDS), was applied to identify and quantify the chemical andmineralogical forms of Cu, Ni, Fe, Mn, Zn, Pb, Cr and Cd presentin the topsoil from a mining and smelting area near Sudbury (Ontario, Canada). The possible mobility of the chemical forms was also assessed. The metal fractions: (1) soluble and exchangeable, (2) occluded in manganese oxides and in easily reducible iron oxides, (3) organically bound and in form of sulphides, (4) residual mainly present in the mineral lattice structures were separated. Cu and Ni were the major metallic contaminants, occurring in soils in broad ranges of concentrations: Cu 11–1890 and Ni 23–2150 mg kg^-1. Cu was uniformly distributed among allthe extracted fractions. Ni was found associated mainly withthe residual forms, accounting for 17–92%, with an averageof 64%, of the total Ni present in the soils. Fe, Mn, Zn,Pb, Cr and Cd, while occurring in most analysed samples innormal soil concentrations, were primarily held in theresidual mineral fraction (on average >50%). The solubleand exchangeable forms made a small contribution (≤8.1%)to the total content of metals extracted. At least 14% ofthe total Cd, Mn and Pb was mobilised from the reducibleforms. The oxidizable fraction assumed mean values higher than10% only for Pb and Zn. Statistical treatment of the experimental data showed significant correlations between totalmetal content of the soils, some soil properties such as pH value, clay and organic matter content, and metal concentrationsin the various fractions. SEM/EDS analysis showed Fe in form ofoxides and sulphides in soils and Cu, Ni, Mn, Zn and Cr in association with iron oxides. Numerous black carbonaceous particles and precipitates of aluminium fluoride salts, observedin the solid residue left after `total’ digestion, were found tocontain Fe, Ni and Cr.     

Pollution assessment and spatial variation of soil heavy metals in Lixia River Region of Eastern China

Purpose

The effect of soil heavy metals on crops and human health is an important research topic in some fields (Agriculture, Ecology et al.). In this paper, the objective is to understand the pollution status and spatial variability of soil heavy metals in this study area. These results can help decision-makers apportion possible soil heavy metal sources and formulate pollution control policies, effective soil remediation, and management strategies.

Materials and methods

A total of 212 topsoil samples (0–20 cm) were collected and analyzed for eight heavy metals (Cd, Hg, As, Cu, Pb, Cr, Zn, and Ni) from agricultural areas of Yingbao County in Lixia River Region of Eastern China, by using four indices (pollution index (PI), Nemerow pollution index (PI_N), index of geo-accumulation (I _geo), E _i /risk index (RI)) and cluster analysis to assess pollution level and ecological risk level of soil heavy metals and combining with geostatistics to analyze the concentration change of heavy metals in soils. GS+ software was used to analyze the spatial variation of soil heavy metals, and the semi-variogram model is the main tool to calculate the spatial variability and provide the input parameters for the spatial interpolation of kriging. Arcgis software was used to draw the spatial distribution of soil heavy metals.

Results and discussion

The result indicated that the eight heavy metals in soils of this area had moderate variations, with CVs ranging from 23.51 to 64.37 %. Single pollution index and Nemerow pollution index showed that about 2.7 and 1.36 % of soil sampling sites were moderately polluted by Cd and Zn, respectively. The pollution level of soil heavy metals decreased in the order of Cd?>?Zn?>?Pb?>?As?>?Cu?>?Cr?>?Ni?>?Hg. The I _geo values of heavy metals in this area decreased in the order of Zn?>?Cd?>?As?>?Pb?>?Cu?>?Cr?>?Hg?>?Ni. According to the E _i index, except Cd that was in the moderate ecological risk status, other heavy metals in soils were in the light ecological risk status, and the level of potential ecological risk (RI) of soil sampling sites of the whole area was light.

Conclusions

The results of four indices and the analysis of spatial variation indicated that the contents of Cd and Zn were contributed mainly by anthropogenic activities and located in the south-east of this study area. However, the contents of Hg, As, Cu, Pb, Cr, and Ni in soils were primarily influenced by soil parent materials.

     

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

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

Standards for the contents of heavy metals and metalloids in soils

In line with the present-day ecological and toxicological data obtained by Dutch ecologists, heavy metals/metalloids form the following succession according to their hazard degree in soils: Se > Tl > Sb > Cd > V > Hg > Ni > Cu > Cr > As > Ba. This sequence substantially differs from the succession of heavy elements presented in the general toxicological GOST (State Norms and Standards) 17.4.1.02-8, which considers As, Cd, Hg, Se, Pb, and Zn to be strongly hazardous elements, whereas Co, Ni, Mo, Sb, and Cr to be moderately hazardous. As compared to the general toxicological approach, the hazard of lead, zinc, and cobalt is lower in soils, and that of vanadium, antimony, and barium is higher. The new sequence also differs from that of the metal hazard in soils according to the Russian standard on the maximal permissible concentration of mobile metal forms (MPC_mob): Cu > Ni > Co > Cr > Zn. Neither an MPC_mob nor an APC_mob has been adopted for strongly hazardous thallium, selenium, and vanadium in Russia. The content of heavy metals in contaminated soils is very unevenly studied: 11 of them, i.e., Cu, Zn, Pb, Ni, Cd, Cr, As, Mn, Co, Hg, and Se, are better known, while the rest, much worse, although there are dangerous elements (Ba, V, Tl) among them.     

Competitive sorption of cadmium and lead in acid soils of Central Spain

The bioavailability and ultimate fate of heavy metals in the environment are controlled by chemical sorption. To assess competitive sorption of Pb and Cd, batch equilibrium experiments (generating sorption isotherms) and kinetics sorption studies were performed using single and binary metal solutions in surface samples of four soils from central Spain. For comparisons between soils, as well as, single and binary metal solutions, soil chemical processes were characterized using the Langmuir equation, ionic strength, and an empirical power function for kinetic sorption. In addition, soil pH and clay mineralogy were used to explain observed sorption processes. Sorption isotherms were well described by the Langmuir equation and the sorption kinetics were well described by an empirical power function within the reaction times in this study. Soils with higher pH and clay content (characterized by having smectite) had the greatest sorption capacity as estimated by the maximum sorption parameter (Q) of the Langmuir equation. All soils exhibited greater sorption capacity for Pb than Cd and the presence of both metals reduced the tendency for either to be sorbed although Cd sorption was affected to a greater extent than that of Pb. The Langmuir binding strength parameter (k) was always greater for Pb than for Cd. However, these k values tended to increase as a result of the simultaneous presence of both metals that may indicate competition for sorption sites promoting the retention of both metals on more specific sorption sites. The kinetic experiments showed that Pb sorption is initially faster than Cd sorption from both single and binary solutions although the simultaneous presence of both metals affected the sorption of Cd at short times while only a minor effect was observed on Pb. The estimated exponents of the kinetic function were in all cases smaller for Pb than for Cd, likely due to diffusion processes into micropores or interlayer space of the clay minerals which occurs more readily for Cd than Pb. Finally, the overall sorption processes of Pb and Cd in the smectitic soil with the highest sorption capacity of the studied soils are slower than in the rest of the soils with a clay mineralogy dominated by kaolinite and illite, exhibiting these soils similar sorption rates. These results demonstrate a significant interaction between Pb and Cd sorption when both metals are present that depends on important soil properties such as the clay mineralogy.     

Adsorption isotherms of copper and zinc in clay minerals of calcareous soils and their effects on X-ray diffraction

Reactions of elements with the water mineral interface are important and affect their bioavailability and transportation within soil. Effects of metal sorption on X-ray-diffraction (XRD-photographs) of clay minerals have been not studied. Therefore, sorption experiments were done on clay fractions of two calcareous soils using 12 concentrations of 0–2000 mg L^?1 Zn(NO₃)₂ and Cu(NO₃)₂. Langmuir and Freundlich isotherms’ coefficients were determined. After sorption, XRD-diffraction were prepared and compared with those of initial samples. Langmuir (R² = 0.996–0.999 and SE = 0.001–0.002) and Freundlich equation were the best-model for Zn and Cu-sorption, respectively. Sorption energy was higher for Zn than Cu, whereas the maximum concentration of sorbed-Cu was higher than that of Zn. Distribution coefficient (K_d) of Cu were more (threefold) than that of Zn. The K_d values representing the slope of Freundlich isotherms decreased according to linear regression equations (R² = 0.72–0.91) as the equilibrium concentrations of metals increased. No significant differences were observed among XRD-photographs of applied concentrations (some negligible differences were found in position/sharpness of peaks). Dry-XRD-method resulted in omission of intensity peaks at 2θ which may interfere in recognition of clays that show a maximum intensity >1.4 nm in the mentioned 2θ. Zinc can become more leachable especially in Shekarbani-soil-series, whereas, Cu highly adsorb on clay minerals and can show less tendency to transportation.     

The adsorption characteristics of soils and removal of cadmium and nickel from wastewaters

The interactions between the adsorption characteristics of 27 experimental soils and the sorption of Cd and Ni from the municipal wastewaters were investigated in this study. The removal of these elements from soil solution was followed for 50 days. All the adsorption characteristics, except cation exchange capacity and organic matter, were significantly correlated to the sorption of Cd after one day shaking. After 7 days of shaking, none of the soil adsorption characteristics except free CaCO₃ was significantly correlated to Cd removal from wastewater. The soil saturated paste pH and suspension pH were strongly correlated to Cd sorption throughout this experiment. The behavior of Ni in soils was different from that of Cd. Surface area, total Fe, and total Al were significantly correlated to Ni sorption. The correlation between Ni removal and pH was the strongest than any other parameter studied. After 7 days shaking, clay content and total Ca were not significantly correlated to Ni sorption. The cation exchange capacity of the soils was not significantly correlated to Cd or Ni sorption in this experiment. It seems that in the experimental soils, concentration of Cd and Ni were probably not controlled by adsorption process. The precipitation process was probably playing a major role in the removal of these elements from the municipal wastewaters. As observed in this experiment, the cation exchange capacity of experimental soils was a poor parameter to define sorption capacity of these soils for Cd and Ni. The guidelines for determining the soil sludge load, which are mainly based on the cation exchange capacity of soils, should be revised.     

Inhibitory effects of the total and water-soluble concentrations of nine different metals on the dehydrogenase activity of a loess soil

 This study focuses on a comparison of the microbial toxicity of nine metals, including As as a metalloid and two species of Cr. A loess soil [Ap horizon, clay 15.2%, organic C 1.12%, pH(CaCl₂) 7.02] was spiked with 8–12 geometrically increasing doses of the metals. The dehydrogenase assay (2-p-iodophenyl-3-p-nitrophenyl-5-phenyltetrazoliumchloride method) was combined with sorption and solubility experiments. The resulting dose-response curves and sorption isotherms were used to derive total doses that caused definite percentage inhibitions [i.e. effective doses (ED) causing a 10–90% reduction in dehydrogenase activity (dha)] as well as the corresponding toxic solution concentrations causing the same reductions in dha (i.e. effective concentrations; EC₁₀–EC₉₀). Based on total doses, the toxicity decreased in the following order with ED₅₀ values (mg kg^–1) given in brackets: Hg (2.0)>Cu (35)>Cr(VI) (71)>Cr(III) (75)>Cd (90)>Ni (100)>Zn (115)>As (168)>Co (582)>Pb (652). With regard to solution concentrations, toxicity decreased in the order (EC₅₀ in mg l^–1): Hg (0.003)>Pb (0.04)>Cu (0.05)>Cd (0.14)>Zn (0.19)>Cr(III) (0.62)>Ni (0.69)>Co (30.6)>As (55.5)>Cr(VI) (78.1). The retention of the metals by the soil differed strongly. Pb, Cu, and Hg exhibited the highest and Ni, As, and Cr(VI) the lowest sorption constants (Freundlich K values: 2455, 724, 348, 93, 13, and 0.06 mg kg^–1, respectively). The sorptivity of the metals and their microbial toxicity in the aqueous phase were characteristically related: metals with a strong toxic action in the soil solution were adsorbed by the soil to a high degree and vice versa. Therefore, especially for metals with a high inherent toxicity, sorption is an effective way of immobilizing them and temporarily detoxifying soil. Received: 2 July 1998     

Sorption of lead,copper, zinc,and cadmium by soils: effect of nitriloacetic acid on metal retention

Abstract

Laboratory experiments were carried out to evaluate lead (Pb), copper (Cu), zinc (Zn), and cadmium (Cd) sorption‐desorption by three soils of contrasting characteristics. Talamanca (silt loam, montmorillonite, Calcic Haploxeralfs), Mazowe (clay, kaolinite, Rhodic Kandiustalf), and Realejos (sandy silt loam, allophane, Typic Hapludands). A second objective was to study the effect of nitriloacetic acid (NTA) on the sorption process. The Talamanca soil, which had a native pH of 6.4 and presented the highest effective cation exchange capacity (ECEC), sorbed more of each of the metal tested than did the other two soils. When the other two soils were compared metal sorption was also related to pH and ECEC. The very low sorption capacity showed by Realejos may be attributed to the low net surface negative charge density of this soil, arising from its allophanic nature. A common feature of the three soils was the relative strong sorption of both Pb and Cu relative to Cd and Zn with Pb showing the highest sorption levels. The selectivity sequences of metals retention were Pb>Cu>Zn>Cd for Talamanca soil, Pb>Cu>Zn≈Cd for Mazowe, and Pb>Cu>Cd>Zn for Realejos. Metal desorption values were low. The order of metal desorption (Cd≈Zn>Cu>Pb) was the same for the three soils studied. Quantitative differences observed in the extractability of the sorbed metals between the soils (Realejos>Mazowe>Talamanca) indicated that soil properties which enhanced metal sorption contributed at the same time to slow down the backward reaction. The addition of NTA to the soil suspension significantly depressed metal sorption by the three soils investigated. Compared with the free ligand system Pb, Cu, Zn, and Cd sorption in the presence of NTA decreased roughly 50%.     

Modelling trace metal extractability and solubility in French forest soils by using soil properties

Soil/solution partitioning of trace metals (TM: Cd, Co, Cr, Cu, Ni, Sb, Pb and Zn) has been investigated in six French forest sites that have been subjected to TM atmospheric inputs. Soil profiles have been sampled and analysed for major soil properties, and CaCl₂‐extractable and total metal content. Metal concentrations (expressed on a molar basis) in soil (total), in CaCl₂ extracts and soil solution collected monthly from fresh soil by centrifugation, were in the order: Cr > Zn > Ni > Cu > Pb > Co > Sb > Cd , Zn > Cu > Pb = Ni > Co > Cd > Cr and Zn > Ni > Cu > Pb > Co > Cr > Cd > Sb , respectively. Metal extractability and solubility were predicted by using soil properties. Soil pH was the most significant property in predicting metal partitioning, but TM behaviour differed between acid and non‐acid soils. TM extractability was predicted significantly by soil pH for pH < 6, and by soil pH and Fe content for all soil conditions. Total metal concentration in soil solution was predicted well by soil pH and organic carbon content for Cd, Co, Cr, Ni and Zn, by Fe content for Cu, Cr, Ni, Pb and Sb and total soil metal content for Cu, Cr, Ni, Pb and Sb, with a better prediction for acidic conditions (pH < 6). At more alkaline pH conditions, solute concentrations of Cu, Cr, Sb and Pb were larger than predicted by the pH relationship, as a consequence of association with Fe colloids and complexing with dissolved organic carbon. Metal speciation in soil solutions determined by WHAM‐VI indicated that free metal ion (FMI) concentration was significantly related to soil pH for all pH conditions. The FMI concentrations of Cu and Zn were well predicted by pH alone, Pb by pH and Fe content and Cd, Co and Ni by soil pH and organic carbon content. Differences between soluble total metal and FMI concentrations were particularly large for pH < 6. This should be taken into account for risk and critical load assessment in the case of terrestrial ecosystems.