Modelling field-scale cadmium transport below the root zone of a sewage sludge amended soil in an arid region in Central Iran

Addition of trace metals such as cadmium to soils in metal-rich sewage sludge may result in contamination of soil and groundwater. This study addresses the plot-scale transport of Cd derived from sewage sludge in a layered clay soil in an arid region of central Iran. Sewage sludge was enriched by Cd at rates of 38 and 80 mg kg(-1) and applied to experimental soil plots using a complete random block design with three replicates. Cadmium concentration was measured as a function of depth after 185 and 617 days. HYDRUS-1D and MACRO codes were calibrated for Cd transport in the site treated with 80 mg kg(-1) sewage sludge. Model parameters were estimated by inverse modelling using the SUFI-2 procedure. The site treated with 38 mg kg(-1) cadmium was used to test the calibrated models. Both convection-dispersion equation (CDE) and non-equilibrium CDE in HYDRUS-1D produced reasonable calibration results. However, the estimated Freundlich sorption constants were significantly smaller than those measured in a batch study. A site tracer experiment revealed the existence of substantial macropore flow. For this reason we applied MACRO to account for this process. The calibration and test results with MACRO were as good as those obtained by HYDRUS-1D with the difference that adsorption constants were much closer to the measured ones. This indicates that in HYDRUS-1D, the adsorption parameters were underestimated in order to allow a deeper transport of Cd which had actually occurred due to macropore flow. A 20-year simulation scenario depicting the long-term effect of sludge application indicated small risk of groundwater contamination. However, high concentration of Cd near the soil surface raises a concern about the crop Cd uptake which should be further investigated.     

Cadmium uptake by tobacco as affected by liming, N form, and year of cultivation

Tobacco is able to accumulate cadmium and reduction of cadmium content can reduce health hazards to smokers. Soil pH and form of N fertilizers are among the factors affecting Cd uptake by tobacco. This hypothesis was tested in an acid soil in northern Greece by a four year field experiment. The variability of Cd uptake by tobacco was attributed to the variation of soil Cd availability as affected by soil pH. Liming with 3000 kg Ca(OH)(2) ha(-1) increased soil pH by 0.8 units and decreased extractable with DTPA soil and leaf Cd by 40% and 35%, respectively. The ammonium fertilizer caused the opposite, but weaker, effects. Liming reduced soil Cd more in the ammonium treatment than in nitrate or combined N treatments. The year of cultivation strongly affected soil and leaf Cd. Four years after tobacco cultivation, soil pH was reduced by 0.5 units, whereas soil and leaf Cd reduction was more than 60% in the limed treatments. Liming affected Cd uptake only in the first three years of cultivation.     

Chemical methods and phytoremediation of soil contaminated with heavy metals

The effects of chemical amendments (calcium carbonate (CC), steel sludge (SS) and furnace slag (FS)) on the growth and uptake of cadmium (Cd) by wetland rice, Chinese cabbage and wheat grown in a red soil contaminated with Cd were investigated using a pot experiment. The phytoremediation of heavy metal contaminated soil with vetiver grass was also studied in a field plot experiment. Results showed that treatments with CC, SS and FS decreased Cd uptake by wetland rice, Chinese cabbage and wheat by 23-95% compared with the unamended control. Among the three amendments, FS was the most efficient at suppressing Cd uptake by the plants, probably due to its higher content of available silicon (Si). The concentrations of zinc (Zn), lead (Pb) and Cd in the shoots of vetiver grass were 42-67%, 500-1200% and 120-260% higher in contaminated plots than in control, respectively. Cadmium accumulation by vetiver shoots was 218 g Cd/ha at a soil Cd concentration of 0.33 mg Cd/kg. It is suggested that heavy metal-contaminated soil could be remediated with a combination of chemical treatments and plants.     

Cadmium effect on the structure of supra- and subpharyngeal ganglia and the neurosecretory processes in earthworm Dendrobaena veneta (Rosa)

Cadmium effects on the supra- and subpharyngeal ganglia, neurosecretion and RNA content in the neurosecretory cells were tested in earthworms Dendrobaena veneta exposed to 10 and 50 mg Cd kg(-1) in soil after 20 days of the experiment. Accumulation of cadmium in the ganglia of nervous system was also measured using AAS method. Cadmium was accumulated in the nervous system. The accumulated amount was proportional to Cd soil concentration and the exposure time. A considerable fall in neurosecretion and RNA content in the neurosecretory cells and neurosecretion in the neuropile (the axons) of both tested ganglia was induced by 50 mg Cd kg(-1). It seemed that neurosecretion synthesis and its axonal transport could be suppressed. Cadmium caused degenerative changes as vacuolization of the neurosecretory cells and neuropile in both tested ganglia.     

Remediation of contaminated agricultural soils near a former Pb/Zn smelter in Austria: batch, pot and field experiments

Metal contaminated crops from contaminated soils are possible hazards for the food chain. The aim of this study was to find practical and cost-effective measures to reduce metal uptake in crops grown on metal contaminated soils near a former metal smelter in Austria. Metal-inefficient cultivars of crop plants commonly grown in the area were investigated in combination with in-situ soil amendments. A laboratory batch experiment using 15 potential amendments was used to select 5 amendments to treat contaminated soil in a pot study using two Barley (Hordeum vulgare L.) cultivars that differed in their ability to accumulate cadmium. Results from this experiment identified 3 of these amendments for use in a field trial. In the pot experiment a reduction in ammonium nitrate extractable Cd (<41%) and Pb (<49%) compared to the controls was measured, with a concurrent reduction of uptake into barley grain (Cd<62%, Pb<68%). In the field extractable fractions of Cd, Pb, and Zn were reduced by up to 96%, 99%, and 99%, respectively in amended soils.     

Modeling solute transport in one-dimensional homogeneous and heterogeneous soil columns with continuous time random walk

In this paper, we used the continuous time random walk (CTRW) framework to characterize the transport process in 1250-cm long one-dimensional homogenous and heterogeneous soil columns at the experiments conducted by Huang et al. [Huang, K., Toride, N., van Genuchten, M.Th., 1995. Experimental investigation of solute transport in large, homogeneous and heterogeneous, saturated soil columns. Trans. Porous Media. 18, 283-302]. The transport process was also simulated by using the advection-dispersion equation (ADE) and the spatial fractional advection-dispersion equation (FADE) for comparison. In the homogeneous soil column, the non-Fickian behavior is found at the distances less than 1000cm with beta values larger than 1.60, but less than 2, and Fickian form transport is obtained at distances larger than 1000cm with beta values larger than 2. In the heterogeneous soil column, we found the most anomalous behavior at distances from 200cm to 700cm with beta values ranging from 0.894 to 0.958, and non-Fickian transport process is observed at distances larger than 800cm with beta values in the range between 1 and 1.3. More significant non-Fickian behavior is found for transport in the heterogeneous soil column than that in the homogeneous soil column. The CTRW fits to the breakthrough curves (BTCs) have lower values of root mean square error (RMSE) and higher values of determination coefficient (r(2)), with respect to the fits of ADE and FADE. The CTRW model also is better captures the full evolution of BTCs, and especially their tails.     

Identification of rice cultivar with exclusive characteristic to Cd using a field-polluted soil and its foreground application

Using low-accumulative plant, especially excluder crop, to safely produce food is one of the very important technologies of phytoremediation, which is practical to safe production and long-term remediation of heavy metal-contaminated soil. A pot experiment using field cadmium (Cd)-contaminated soil (Cd concentration was 0.75 mg?kg^?1) was conducted to compare Cd accumulation differences among 39 normal rice cultivars (Japonica) in Shenyang region of China for food safety and high grain yield aim. The results showed that brown grain Cd concentration in 12 rice cultivars of a total of 39 tested cultivars was lower than 0.2 mg?kg^?1 (Agricultural Trade Standard of Nonpollution Food for Rice of China, NY 5115–2008). In these 12 cultivars, Cd enrichment factors (Cd concentration ratio in shoot to that in soil) of nine cultivars were lower than 1. Likewise, Cd translocation factors (Cd concentration ratio in shoot to that in root) of eight cultivars were lower than the 0.28 average. Furthermore, grain yield per pot of seven cultivars were higher than the average 18.4 g?pot^?1. Four cultivars, i.e., Shendao 5, Tianfu 1, Fuhe 90, and Yanfeng 47 showed Cd-exclusive characteristic and better foreground application.     

The influence of long-term fertilization on cadmium (Cd) accumulation in soil and its uptake by crops

Continuous application of organic and inorganic fertilizers can affect soil and food quality with respect to heavy metal concentrations. The risk of cadmium (Cd) contamination in a long-term (over 20 years) experimental field in North China with an annual crop rotation of winter wheat and summer maize was investigated. The long-term experiment had a complete randomized block design with seven fertilizer treatments and four replications. The seven fertilizer treatments were (1) organic compost (OM), (2) half organic compost plus half chemical fertilizer (OM?+?NPK), (3) NPK fertilizer (NPK), (4–6) chemical fertilizers without one of the major nutrients (NP, PK, and NK), and (7) an unamended control (CK). Soil samples from 0 to 20 cm were collected in 1989, 1999, and 2009 to characterize Cd and other soil properties. During the past 20 years, various extents of Cd accumulation were observed in the soil, and the accumulation was mainly affected by atmospheric dry and wet deposition and fertilization. In 2009, the average Cd concentration in the soil was 148?±?15 μg kg^?1 and decreased in the order of NPK?≈?OM?+?NKP?≈?PK?>?NP?≈?NK?>?OM?≈?CK. Sequential extraction of Cd showed that the acid-soluble fraction (F1, 32?±?7 %) and the residual fraction (F4, 31?±?5 %) were the dominant fractions of Cd in the soil, followed by the reducible fraction (F2, 22?±?5 %) and oxidizable fraction (F3, 15?±?6 %). The acid-soluble Cd fraction in the soil and Cd accumulation in the crops increased with soil plant available K. Fraction F3 was increased by soil organic C (SOC) and crop yields, but SOC reduced the uptake of soil Cd by crops. The long-term P fertilization resulted in more Cd buildup in the soil than other treatments, but the uptake of Cd by crops was inhibited by the precipitation of Cd with phosphate in the soil. Although soil Cd was slightly increased over the 20 years of intensive crop production, both soil and grain/kernel Cd concentrations were still below the national standards for environmental and food safety.     

A comparative study of cadmium phytoextraction by accumulator and weed species

Phytoextraction has shown great potential as an alternative technique for the remediation of metal contaminated soils. The objective of this study was to investigate cadmium (Cd) phytoextraction ability of high biomass producing weeds in comparison to indicator plant species. The pot study conducted with 10 to 200 mg Cd kg(-1) soil indicated that Ipomoea carnea was more effective in removing Cd from soil than Brassica juncea. Among the five species, B. juncea accumulated maximum Cd, but I. carnea followed by Dhatura innoxia and Phragmytes karka were the most suitable species for phytoextraction of cadmium from soil, if the whole plant or above ground biomass is harvested. In the relatively short time of this experiment, I. carnea produced more than 5 times more biomass in comparison to B. juncea. There were significant differences (p < 0.05) between the shoot length and shoot mass of control and treated plants.     

Characterization of H+ and Cd2+ binding properties of the bacterial exopolysaccharides

The proton and Cd binding capacities of microbially produced exopolysaccharides, EPS, were quantified by the determination of stability constants and the concentration of complexing sites using H(+) or Cd(2+) selective electrodes in dynamic titrations. The influence of ionic strength, pH and the Cd to EPS ratio was evaluated over large concentration ranges. The applicability of the non-ideal competitive adsorption isotherm combined with a Donnan electrostatics approach was tested with respect to the EPS. Proton and cadmium binding data were compared with literature data examining other ubiquitous environmental ligands including humic substances, alginate, bacteria, etc. Subsequent modelling of Cd speciation in aquatic (fresh and marine waters) and soil systems suggested that the exopolysaccharides would play non-negligible role, under most conditions. The quantitative information provided in this paper thus represents an important advance in our understanding of Cd transport, bioavailability and impact in aquatic and terrestrial systems.     

外源Cd对不同利用方式红壤脲酶活性的影响

采用室内培养实验,通过将外源Cd添加到同一母质、全镉含量相近的不同利用方式的红壤中(林地、水稻土和菜园土),研究了外源Cd污染对不同利用方式红壤脲酶活性的影响。结果表明:整个培养过程中,Cd污染对3种红壤脲酶活性都有抑制作用,且随重金属浓度的增强而增强。同剂量Cd污染对3种红壤脲酶活性的抑制效应不同,大小为林地>水稻土>菜园土。实验设定的Cd处理水平下,对林地、水稻土和菜园土脲酶活性产生显著抑制作用(p<0.05)的Cd浓度分别为5、30和50 mg/kg土。     

Interaction of polycyclic aromatic hydrocarbons and heavy metals on soil enzyme

Actions and interactions of heavy metals (cadmium, zinc and plumbum) and polycyclic aromatic hydrocarbons (PAHs) [phenanthrene, fluoranthene, benzo(a)pyrene] on the soil urease and dehydrogenase activity were studied after 49 days exposure. The experimental approach was based on the uniform design which can cut the experiment time and improve the efficiency of experiments. Data treatment was essentially based on the multiple regression technique. The results showed that the action and interaction between heavy metals and PAHs were strongly dependent on the time of pollution. The dehydrogenase exhibits more sensitive to the combined pollution than urease. The negative interaction between Zn and Cd to hydrogenase activity and the combined stimulatory activity of Phenanthrene and Benzo(a)pyrene (or fluoranthene) to soil enzyme were observed. The interactions between Zn (Cd) and phenanthrene towards urease (dehydrogenase) were positive, and the interaction between Zn and benzo(a)pyrene to urease activity was negative. This study corresponds to exploratory phase in order to reveal interaction effects of heavy metals and PAHs on the soil enzyme and then to set up more in-depth analysis to increase progressively the understanding of the ecotoxicological mechanisms involved.     

Enhanced transport of pesticides in a field trial with treated sewage sludge

This study was designed to provide high-density data on spatial distribution of three herbicides with different physiochemical characteristics in a sludge-amended and non-amended control field over the course of an irrigation season. The field experiment was carried out on a sandy loam Hamra Red Mediterranean soil (Rhodoxeralf) at Bet Dagan, Israel. After a single 50 mm irrigation event, the mean centers of mass (COM) in the control field were at 15.6, 14.9, and 17 cm for bromacil, atrazine and terbuthylazine, respectively; in the sludge-amended field, mean COMs were at 28.8, 31.2, and 34.1 cm, respectively. After 500 mm of irrigation in the control field, the COM depth distribution of the three pesticides was inversely correlated with octanol-water (Kow) distribution coefficients and soil sorption coefficients (Koc), and positively correlated with aqueous solubilities. After 500 mm irrigation in the sludge-amended field, the mean terbuthylazine COM was at 19.8 cm versus 13.8 cm for the control field, demonstrating a sustained enhanced effect on terbuthylazine transport. Downward transport of atrazine was also enhanced by sludge amendment, albeit less than terbuthylazine. Bromacil was preferentially accumulated in the upper soil layers of the sludge-amended field as compared with the control field after 500 mm irrigation. The enhanced transport of all three pesticides in the sludge-amended field after a single irrigation event is attributed to development of preferential flow pathways around hydrophobic clods of sludge. Enhanced transport of terbuthylazine, and to a lesser extent, atrazine, throughout the irrigation season, is attributed to their transport as complexes with dissolved, colloidal and suspended organic matter derived from sludge degradation.     

Physiological mechanism of plant roots exposed to cadmium

Physiological experiments on plant roots exposed to cadmium were conducted on carrot and radish using a liquid culture and a pot experiment with a series of cadmium applications. Activities of four enzymes (catalase, peroxidase, polyphenol oxidase, superoxide dismutase), and concentrations of free proline and malonaldehyde in the roots of both plants were investigated. Results showed that the germination rate and growth of roots of both plants were inhibited at the concentration of 20 mg Cd/l, and the inhibition was increased with the increasing concentrations of cadmium, both in the liquid culture and in the pot experiment; activities of the four enzymes declined similarly in both species. The concentration of proline in roots reached the maximum when the application of cadmium was at the level of 20 mg/l in the liquid culture (or 20 mg/kg in soil), and then it declined slowly with the increasing concentration of cadmium. However, the reverse trend was observed for the concentration of malonaldehyde. All of bio-indicators measured here was quite sensitive to the addition of cadmium.     

The influences of fly ash on stabilization for Cd in contaminated soils

Soil contaminated with potentially toxic metals (PTMs) has being a global environmental issue, which needs to be addressed on the priority basis. Fly ash (FA) is a kind of low-cost alkaline materials, which has been widely used in remediation of soil contaminated by PTMs, while the effects of FA on the stability for PTMs in contaminated farmland soil are still not clearly evaluated. In this study, cadmium (Cd) contaminated soil samples, collected from Shaanxi (SX), Hubei (HB), and Zhejiang (ZJ) province of China, were amended with FA addition (0, 1%, 2.5%, 5%, and 10% dose), and 1-year changes of Cd availability in soil samples were focused on. In addition, biological assessment method through pot culture was carried out to evaluate the reuse potential of Cd contaminated soils amended by FA. The result indicated that FA had a notable impact on decreasing the Cd mobility of SX soil (sand type), with 18.2~52.1% reduction in the DTPA extractable solution, followed by HB soil with 5.9~16.7% reduction, but no obvious effect of FA on ZJ soil (clay type) was observed. Furthermore, the results of pot experiment revealed that FA application could increase the biomass of Chinese cabbage. However, the DTPA extractable Cd in soils after planation and the Cd accumulation of plant increased. The results revealed that FA was not a promising soil stabilizer to immobilize HMs in Cd contaminated soil, and careful consideration should be given to Cd contaminated soils with FA restoration especially in their using for farmland productive due to the remaining risk of Cd bioavailability. These results also contributed to provide references for similar soil pollution remediation.

     

Heavy metal accumulation by poplar in calcareous soil with various degrees of multi-metal contamination: implications for phytoextraction and phytostabilization

The object of this study was to assess the capacity of Populus alba L. var. pyramidalis Bunge for phytoremediation of heavy metals on calcareous soils contaminated with multiple metals. In a pot culture experiment, a multi-metal-contaminated calcareous soil was mixed at different ratios with an uncontaminated, but otherwise similar soil, to establish a gradient of soil metal contamination levels. In a field experiment, poplars with different stand ages (3, 5, and 7 years) were sampled randomly in a wastewater-irrigated field. The concentrations of cadmium (Cd), Cu, lead (Pb), and zinc (Zn) in the poplar tissues and soil were determined. The accumulation of Cd and Zn was greatest in the leaves of P. pyramidalis, while Cu and Pb mainly accumulated in the roots. In the pot experiment, the highest tissue concentrations of Cd (40.76 mg kg^?1), Cu (8.21 mg kg^?1), Pb (41.62 mg kg^?1), and Zn (696 mg kg^?1) were all noted in the multi-metal-contaminated soil. Although extremely high levels of Cd and Zn accumulated in the leaves, phytoextraction using P. pyramidalis may take at least 24 and 16 years for Cd and Zn, respectively. The foliar concentrations of Cu and Pb were always within the normal ranges and were never higher than 8 and 5 mg kg^?1, respectively. The field experiment also revealed that the concentrations of all four metals in the bark were significantly higher than that in the wood. In addition, the tissue metal concentrations, together with the NH₄NO₃-extractable concentrations of metals in the root zone, decreased as the stand age increased. P. pyramidalis is suitable for phytostabilization of calcareous soils contaminated with multiple metals, but collection of the litter fall would be necessary due to the relatively high foliar concentrations of Cd and Zn.     

Dissipation of available benzo[a]pyrene in aging soil co-contaminated with cadmium and pyrene

A microcosm experiment was conducted to investigate the dissipation of available benzo[a]pyrene (BaP) in soils co-contaminated with cadmium (Cd) and pyrene (PYR) during aging process. The available residue of BaP in soil was separated into desorbing and non-desorbing fractions. The desorbing fraction contributed more to the dissipation of available BaP than the non-desorbing fraction did. The concentration of bound-residue fraction of BaP was quite low across all treatments. Within the duration of this study (250 days), transformation of BaP from available fractions to bound-residue fraction was not observed. Microbial degradation was the dominant mechanism of the dissipation of available BaP in the soil. The dissipation of available BaP was significantly inhibited with the increment in Cd level in the soil. The addition of PYR (250 mg kg^?1) remarkably promoted the dissipation of available BaP without reducing Cd availability in the soil. The calculated half-life of available BaP in the soil prolonged with the increment in Cd level; however, the addition of PYR shortened the half-life of available BaP by 13.1, 12.7, and 32.8 % in 0.44, 2.56, and 22 mg Cd kg^?1 soils, respectively. These results demonstrated that the inhibiting effect of Cd and the promoting effect of PYR on the dissipation of available BaP were competitive. Therefore, this study shows that the bioremediation process of BaP can be more complicated in co-contaminated soils.     

Transfer functions for solid-solution partitioning of cadmium for Australian soils

To assess transport and ecotoxicological risks of metals, such as cadmium (Cd) in soils, models are needed for partitioning and speciation. We derived regression-based “partition-relations” based on adsorption and desorption experiments for main Australian soil types. First, batch adsorption experiments were carried out over a realistic range of dissolved Cd concentrations in agricultural soils in Australia. Results showed linear sorption relationships, implying the adequacy of using Kd values to describe partitioning. Desorption measurements were then carried out to assess in-situ Kd values and relate these to soil properties The best transfer functions for solid-solution partitioning were found for Kd values relating total dissolved Cd concentration to total soil Cd concentrations, accounting for the variation in pH, SOM contents and DOC concentrations. Model predictions compared well with measurements of an independent data set, but there was a tendency to underestimate dissolved Cd concentrations of highly polluted soils.     

Effects of pH on the toxicity of cadmium, copper, lead and zinc to Folsomia candida Willem, 1902 (Collembola) in a standard laboratory test system

EC₅₀s for cadmium, copper, lead and zinc were determined for juvenile production of Folsomia candida at pH6.0, 5.0 and 4.5 in a standard laboratory test system. In contrast to most previous studies where metal toxicity was increased at low pHs, in our experiments there was no clear relationship between soil acidity and EC_{50-reproduction} in this species. The EC_{50-reproduction} values (μg g⁻¹) for cadmium and zinc were similar at all three pHs (pH6.0: Cd 590, Zn 900; pH5.0: Cd 780, Zn 600; pH4.5: Cd 480, Zn 590). In contaminated field sites adjacent to primary zinc smelters, zinc is invariably present in soils at concentrations of at least 50 times that of cadmium Thus deleterious effects of mixtures of these metals on populations of Collembola in such sites can be attributed to zinc rather than cadmium.     

Mobility of arsenic, cadmium and zinc in a multi-element contaminated soil profile assessed by in-situ soil pore water sampling, column leaching and sequential extraction

Three methods for predicting element mobility in soils have been applied to an iron-rich soil, contaminated with arsenic, cadmium and zinc. Soils were collected from 0 to 30 cm, 30 to 70 cm and 70 to 100 cm depths in the field and soil pore water was collected at different depths from an adjacent 100 cm deep trench. Sequential extraction and a column leaching test in the laboratory were compared to element concentrations in pore water sampled directly from the field. Arsenic showed low extractability, low leachability and occurred at low concentrations in pore water samples. Cadmium and zinc were more labile and present in higher concentrations in pore water, increasing with soil depth. Pore water sampling gave the best indication of short term element mobility when field conditions were taken into account, but further extraction and leaching procedures produced a fuller picture of element dynamics, revealing highly labile Cd deep in the soil profile.