Influence of soil pH on the fractionation of Cr, Cu and Zn in solid phases from a landfill site

The spatial variability of soil pH for engineered Weathered Oxford Clay is described using 35 samples collected from the base of a new cell in an existing landfill. Soil pH variability influences the reactivity of Cr, Cu and Zn in the site. The reactivity of these metals as natural components was determined using a sequential extraction method. The total concentration of Cr, Cu and Zn and the mineralogical composition were also determined. The results showed that due to the presence of a layer rich in pyrite in the base, a natural acidification may occur which can produce a soil pH as low as 2.7. The spatial variability of soil pH in this area has been described with an anisotropical variogram model and the estimation of its values at unsampled locations was carried out using the ordinary kriging algorithm. From the spatial modelling of the soil pH, it was found that the metals in the soil solid phases follow a similar distribution.     

Impact of lime-stabilized biosolid application on Cu,Ni, Pb and Zn mobility in an acidic soil

A soil column leaching study was conducted on an acidic soil in order to assess the impact of lime-stabilized biosolid on the mobility of metallic pollutants (Cu, Ni, Pb and Zn). Column leaching experiments were conducted by injecting successively CaCl₂, oxalic acid and ethylenediaminetetraacetic acid (EDTA) solutions through soil and biosolid-amended soil columns. The comparison of leaching curves showed that the transport of metals is mainly related to the dissolved organic carbon, pH and the nature of extractants. Metal mobility in the soil and biosolid-amended soils is higher with EDTA than with CaCl₂ and oxalic acid extractions, indicating that metals are strongly bound to solid-phase components. The single application of lime-stabilized biosolid at a rate ranging from 15 to 30 t/ha tends to decrease the mobility of metals, while repeated applications (2?×?15 t/ha) increase metal leaching from soil. This result highlights the importance of monitoring the movement and concentrations of metals, especially in acid and sandy soils with shallow and smaller water bodies.     

Effect of soil ageing on in vivo arsenic bioavailability in two dissimilar soils

Arsenic (As) bioavailability in spiked soils aged for up to 12 months was assessed using in vitro and in vivo methodologies. Ageing (natural attenuation) of spiked soils resulted in a decline in in vivo As bioavailability (swine assay) of over 75% in soil A (Red Ferrosol) but had no significant effect on in vivo As bioavailability even after 12 months of ageing in soil B (Brown Chromosol). Sequential fractionation, however, indicated that there was repartitioning of As within the soil fractions extracted during the time course investigated. In soil A, the As fraction associated with the more weakly bound soil fractions decreased while the residual fraction increased from 12% to 35%. In contrast, little repartitioning of As was observed in soil B indicating that natural attenuation may be only applicable for As in soils containing specific mineralogical properties.     

底泥生长基质中重金属的迁移特征及生物有效性

河道底泥中重金属含量较高,重金属的迁移性及生物有效性是限制疏浚底泥土地施用或用作废弃场地修复基质资源化利用途径的主要因素。以沈阳细河待疏浚底泥为材料,通过盆栽实验的方法研究了河道底泥与碱性粉煤灰、炉渣和锯木屑配比基质中重金属在紫花苜蓿体内累积、迁移及生物有效性的变化。结果发现,配比底泥基质上紫花苜蓿生物量、株高及株径均好于纯底泥处理,其中底泥、粉煤灰、炉渣、锯木屑以2：0．5：0．5：0．5配比的s2处理中紫花苜蓿生物量是纯底泥处理的11．7倍。与底泥对照相比,配比底泥基质上植株体内重金属含量极显著降低,而且地上部重金属含量显著低于根部含量;底泥基质中紫花苜蓿地上部和根部对Cd、Cu、Pb、Zn的富集系数（BCF）显著低于底泥处理,但转移系数（TF）无显著变化,富集系数（BCF）和转移系数（TF）均小于1．0。紫花苜蓿种植后底泥基质中重金属含量显著低于农用污泥重金属控制标准,除Cd含量略高外,Cu、Pb和Zn含量低于土壤环境质量三级标准。这些结果表明,城市重污染河道底泥经过合理处置后,重金属浓度、活性及生物有效性降低,在其土地施用或废弃地修复中可以用作一些耐性植物的生长基质。     

Geographical and pedological drivers of distribution and risks to soil fauna of seven metals (Cd, Cu, Cr, Ni, Pb, V and Zn) in British soils

Concentrations of seven metals were measured in over 1000 samples as part of an integrated survey. Sixteen metal pairs were significantly positively correlated. Cluster analysis identified two clusters. Metals from the largest (Cr, Cu, Ni, V, Zn), but not the smallest (Cd, Pb) cluster were significantly negatively correlated with spatial location and soil pH and organic matter content. Cd and Pb were not correlated with these parameters, due possibly to the masking effect of recent extensive release. Analysis of trends with soil properties in different habitats indicated that general trends may not necessarily be applicable to all areas. A risk assessment indicated that Zn poses the most widespread direct risk to soil fauna and Cd the least. Any risks associated with high metal concentrations are, however, likely to be greatest in habitats such as arable and horticultural, improved grassland and built up areas where soil metal concentrations are more frequently elevated.     

Microbial indicators of heavy metal contamination in urban and rural soils

Urban soils and especially their microbiology have been a neglected area of study. In this paper, we report on microbial properties of urban soils compared to rural soils of similar lithogenic origin in the vicinity of Aberdeen city. Significant differences in basal respiration rates, microbial biomass and ecophysiological parameters were found in urban soils compared to rural soils. Analysis of community level physiological profiles (CLPP) of micro-organisms showed they consumed C sources faster in urban soils to maintain the same level activity as those in rural soils. Cu, Pb, Zn and Ni were the principal elements that had accumulated in urban soils compared with their rural counterparts with Pb being the most significant metal to distinguish urban soils from rural soils. Sequential extraction showed the final residue after extraction was normally the highest proportion except for Pb, for which the hydroxylamine-hydrochloride extractable Pb was the largest part. Acetic acid extractable fraction of Cd, Cu, Ni, Pb and Zn were higher in urban soils and aqua regia extractable fraction were lower suggesting an elevated availability of heavy metals in urban soils. Correlation analyses between different microbial indicators (basal respiration, biomass-C, and sole C source tests) and heavy metal fractions indicated that basal respiration was negatively correlated with soil Cd, Cu, Ni and Zn inputs while soil microbial biomass was only significantly correlated with Pb. However, both exchangeable and iron- and manganese-bound Ni fractions were mostly responsible for shift of the soil microbial community level physiological profiles (sole C source tests). These data suggest soil microbial indicators can be useful indicators of pollutant heavy metal stress on the health of urban soils.     

The effect of earthworms on the fractionation, mobility and bioavailability of Pb, Zn and Cd before and after soil leaching with EDTA

The effect of two ecologically contrasting earthworm species Eisenia fetida (epigeic) and Octolasion tyrtaeum (endogeic) on the fractionation (accessed using sequential extractions), mobility (toxicity characteristic leaching procedure, TCLP) and oral bioavailability (Ruby's physiologically based extraction test, PBET) of Pb, Zn and Cd was studied before and after soil remediation with soil leaching. Twenty-step leaching, with 2.5 mmol kg(-1) EDTA used in each step, removed 58.4%, 25.0% and 68.0% of initial soil Pb, Zn and Cd, respectively, shifted the fractionation of residual heavy metals toward less labile forms, and decreased their mobility by 83.7%, 80.3%, and 90.9%. Pb oral bioavailability was reduced by 3.1-times (in each stomach and intestinal phase). After soil leaching, both earthworm species enriched the carbonate soil fraction in their casts with residual Pb, and increased the Pb bioavailability in the simulated intestinal phase by a factor of 2.4 (E. fetida) and 2.8 (O. tyrtaeum). The concentration of Pb in TCLP leachate from E. fetida casts was 6.2-times higher than in the bulk of the remediated soil. These results indicate that the effect of biotic factors on the availability of heavy metals residual in soil after soil leaching requires consideration.     

A field method using microcosms to evaluate transfer of Cd,Cu, Ni,Pb and Zn from sewage sludge amended forest soils to Helix aspersa snails

Juvenile Helix aspersa snails exposed in field microcosms were used to assess the transfer of Cd, Cu, Ni, Pb and Zn from forest soils amended with liquid and composted sewage sludge. Zn concentrations and contents were significantly higher in snails exposed to liquid and composted sludge after 5 and 7 weeks of exposure, when compared with control. Trends were less clear for the other metals. Present results show that Zn, among the cocktail of metallic trace elements (MTE) coming from sewage sludge disposal, represents the principal concern for food chain transfer and secondary poisoning risks. The microcosm design used in this experiment was well suited for relatively long-term (about 2 months) active biomonitoring with H. aspersa snails. The snails quickly indicated the variations of MTE concentrations in their immediate environment. Therefore, the present study provides a simple but efficient field tool to evaluate MTE bioavailability and transfer.     

Implications of geographic variability on Comparative Toxicity Potentials of Cu, Ni and Zn in freshwaters of Canadian ecoregions

Current methods of estimating potential environmental impacts of metals in hazard and Life Cycle Impact Assessment (LCIA) do not consider differences in chemistry and landscape properties between geographic sites. Here, we developed and applied a model for regional aquatic impact characterization of metals using an updated method for estimating environmental fate factor (FF), bioavailability factor (BF) and aquatic ecotoxicity factor (EF). We applied the model to analyze differences in Comparative Toxicity Potentials (CTPs) of Cu, Ni and Zn for 24 Canadian ecoregions. The combined impacts of regional variability in ambient chemistry (in particular DOC, pH and hardness) and landscape properties (water residence time) can change the CTPs of these metals for freshwater by up to three orders of magnitude and change the relative ranking of metal hazard between ecoregions. Variation among Canadian freshwater chemistries and landscape characteristics influence the FFs within two orders of magnitude, BFs within two orders of magnitude for Ni and Zn and four orders of magnitude for Cu, and EFs within one order of magnitude. Sensitivity of metal FFs to environmental parameters alone spans three orders of magnitude when a constant water chemistry was used for all ecoregions. These results indicate that application of regionalised metal CTPs can have a significant influence in the analysis of ecotoxicological impacts in the life cycle assessment of products and processes.     

Characteristics of oxytetracycline sorption and potential bioavailability in soils with various physical-chemical properties

Veterinary antibiotics are widely used for disease treatment, prevention and animal growth promoting. Frequent detection of veterinary antibiotics in environments, caused by land application of untreated or even treated antibiotics-containing animal wastes, has posed the growing concern of their adverse effect on natural ecosystems. Oxytetracycline (OTC) is one of the most widely-used veterinary antibiotics in livestock industry. OTC present as a cation, zwitterions, or net negatively charged ion in soils complicates predicting its sorption characteristics and potential bioavailability and toxicity. This study was to identify soil properties influencing OTC sorption and its subsequent bioavailability in five soils with various physical-chemical properties. A solution used to determine bioavailable analytes in soils and sediments, 1 M MgCl₂ (pH 8.5), was chosen to desorb the potentially bioavailable fraction of OTC sorbed onto soils. Our results demonstrated that soils with higher illite content and permanent cation exchange capacity have higher OTC sorption capacity, but increase the availability of sorbed OTC indicated by higher release of sorbed OTC from soils into aqueous phase in 1 M MgCl₂ (pH 8.5). Reversely, soil organic matter (SOM), clay, kaolinite, variable cation exchange capacity, DCB-Fe and -Al have lower OTC sorption capacity, but decrease the release of sorbed OTC from soils into 1 M MgCl₂. These findings indicate that SOM and clay greatly influence OTC adsorption and potential availability. This study contributes significantly to our understanding of the potential bioavailability of sorbed OTC and the effects of soil properties on OTC sorption behaviors in soils.     

Leaching behaviour of Cd, Cu, Pb and Zn in surface soils derived from dredged sediments

Leaching of heavy metals from land-disposed dredged sediment spoils is a potential environmental hazard. The leaching behavior of Cd, Cu, Pb and Zn in surface soils sampled from abandoned dredged sediment disposal sites was assessed. Using simple mass-balance calculations, the significance of the leaching test results with respect to metal migration into underlying clean soil was appraised. The potential leachability, defined as the amounts released at constant pH 4, decreased in the order (% of total contents): Zn (58%) approximately equal to Cd (49%)>Cu (5%) approximately equal to Pb (2%). The kinetics of metal release were determined in a cascade shaking test using de-mineralized water acidified to pH 4 (HNO(3)). Metal concentrations in the leachates were low and metal migration was, assuming uniform convective flow, predicted to be of no environmental concern. It is emphasized that any long-term prediction of metal migration is uncertain.     

Response of Pinus halepensis Mill. seedlings to biosolids enriched with Cu, Ni and Zn in three Mediterranean forest soils

We investigated the response of Pinus halepensis seedlings to the application of biosolids enriched with Cu, Ni and Zn on three Mediterranean forest soils under semiarid conditions. One-year-old seedlings were planted in lysimeters on soils developed from marl, limestone and sandstone which were left unamended, amended with biosolids, or amended with biosolids enriched in Cu, Ni and Zn. Enriched biosolids increased plant heavy metal concentration, but always below phytotoxic levels. Seedlings receiving unenriched biosolids showed a weak reduction in Cu and Zn concentration in needles, negatively affecting physiological status during drought. This effect was alleviated by the application of enriched sludge. Sewage sludge with relatively high levels of Cu, Zn and Ni had minor effects on plant performance on our experimental conditions. Results suggest that micronutrient limitations in these soils may be alleviated by the application of biosolids with a higher Cu, Zn and Ni content than those established by current regulations.     

Effects of Ni, Cr, Hg, Cu, Zn, Al on the dissolved oxygen balance of streams

Inorganic metals besides their direct toxic effects, carry the potential of causing serious variations on existing ecosystems in receiving waters. Self purification mechanism is vital for the continuity of the existing micro and macro living organisms in the streams. This mechanism is effected from the existence of metals. In this study, interferences of HgCl2, HgSO4, Ni(NO3)2, CrCl3, CuSO4.5H2O, K2Cr2O7, ZnSO4.7H2O and Al2(SO4)3.18H2O metal compounds on respirometric BOD and related effects on the self purification, are investigated with the representative formations of DO deficit curves. In the presence of these metals, streamwater BOD parameters and related DO deficit curve formations are significantly effected.     

Evaluation of the content of Zn,Cu, Ni and Pb as well as the enzymatic activity of forest soils exposed to the effect of road traffic pollution

Environmental Science and Pollution Research - The paper evaluates the contents of total forms of selected heavy metals (Zn, Cu, Ni and Pb) as well as the activity of catalase (CAT), dehydrogenases...     

Mobility of Pb, Cu, and Zn in the phosphorus-amended contaminated soils under simulated landfill and rainfall conditions

Phosphorus-bearing materials have been widely applied in immobilization of heavy metals in contaminated soils. However, the study on the stability of the initially P-induced immobilized metals in the contaminated soils is far limited. This work was conducted to evaluate the mobility of Pb, Cu, and Zn in two contrasting contaminated soils amended with phosphate rock tailing (PR) and triple superphosphate fertilizer (TSP), and their combination (P?+?T) under simulated landfill and rainfall conditions. The main objective was to determine the stability of heavy metals in the P-treated contaminated soils in response to the changing environment conditions. The soils were amended with the P-bearing materials at a 2:1 molar ratio of P to metals. After equilibrated for 2 weeks, the soils were evaluated with the leaching procedures. The batch-based toxicity characteristic leaching procedure (TCLP) was conducted to determine the leachability of heavy metals from both untreated and P-treated soils under simulated landfill condition. The column-based synthetic precipitation leaching procedure (SPLP) were undertaken to measure the downward migration of metals from untreated and P-treated soils under simulated rainfall condition. Leachability of Pb, Cu, and Zn in the TCLP extract followed the order of Zn?>?Cu?>?Pb in both soils, with the organic-C- and clay-poor soil showing higher metal leachability than the organic-C- and clay-rich soil. All three P treatments reduced leachability of Pb, Cu, and Zn by up to 89.2, 24.4, and 34.3 %, respectively, compared to the untreated soil, and TSP revealed more effectiveness followed by P?+?T and then PR. The column experiments showed that Zn had the highest downward migration upon 10 pore volumes of SPLP leaching, followed by Pb and then Cu in both soils. However, migration of Pb and Zn to subsoil and leachate were inhibited in the P-treated soil, while Cu in the leachate was enhanced by P treatment in the organic-C-rich soil. More than 73 % P in the amendments remained in the upper 0–10 cm soil layers. However, leaching of P from soluble TSP was significant with 24.3 % of P migrated in the leachate in the organic-C-poor soil. The mobility of heavy metals in the P-treated soil varies with nature of P sources, heavy metals, and soils. Caution should be taken on the multi-metal stabilization since the P amendment may immobilize some metals while promoting others’ mobility. Also, attention should be paid to the high leaching of P from soluble P amendments since it may pose the risk of excessive P-induced eutrophication.     

In vitro and in vivo approaches for the measurement of oral bioavailability of lead (Pb) in contaminated soils: a review

We reviewed the published evidence of lead (Pb) contamination of urban soils, soil Pb risk to children through hand-to-mouth activity, reduction of soil Pb bioavailability due to soil amendments, and methods to assess bioaccessibility which correlate with bioavailability of soil Pb. Feeding tests have shown that urban soils may have much lower Pb bioavailability than previously assumed. Hence bioavailability of soil Pb is the important measure for protection of public health, not total soil Pb. Chemical extraction tests (Pb bioaccessibility) have been developed which are well correlated with the results of bioavailability tests; application of these tests can save money and time compared with feeding tests. Recent findings have revealed that fractional bioaccessibility (bioaccessible compared to total) of Pb in urban soils is only 5-10% of total soil Pb, far lower than the 60% as bioavailable as food-Pb presumed by U.S.-EPA (30% absolute bioavailability used in IEUBK model).     

Enhanced phytoextraction of Cu, Pb, Zn and Cd with EDTA and EDDS

Chemically enhanced phytoextraction has been proposed as an effective approach to removing heavy metals from contaminated soil through the use of high biomass plants. Using pot experiments, the effects of the application of EDTA, EDDS and citric acid on the uptake of Cu, Pb, Zn and Cd by corn (Zea mays L. cv. Nongda 108) and bean (Phaseolus vulgaris L. white bean) plants were studied. The results showed that EDDS was more effective than EDTA at increasing the concentration of Cu in corn and beans. The application of 5 mmol kg-1 soil EDDS to soil significantly increased concentrations of Cu in shoots, with maximum levels of 2060 and 5130 mg kg-1 DW in corn and beans, respectively, which were 45- and 135-fold higher than that in the corresponding control plants to which chelate had not been applied. Concentrations of Zn in shoots were also higher in the plants treated with EDDS than in those treated with EDTA. For Pb and Cd, EDDS was less effective than EDTA. The maximum Cu phytoextraction was found with the EDDS treatment. The application of EDTA and EDDS also significantly increased the shoot-to-root ratios of the concentrations of Cu, Pb, Zn and Cd in both plant species. The results of metal extraction with chelates showed that EDDS was more efficient at solubilizing Cu and Zn than EDTA, and that EDTA was better at solubilizing Pb and Cd than EDDS.     

Dynamic modelling of atmospherically-deposited Ni, Cu, Zn, Cd and Pb in Pennine catchments (northern England)

Simulation modelling with CHUM-AM was carried out to investigate the accumulation and release of atmospherically-deposited heavy metals (Ni, Cu, Zn, Cd and Pb) in six moorland catchments, five with organic-rich soils, one with calcareous brown earths, in the Pennine chain of northern England. The model considers two soil layers and a third layer of weathering mineral matter, and operates on a yearly timestep, driven by deposition scenarios covering the period 1400-2010. The principal processes controlling heavy metals are competitive solid-solution partitioning of solutes, chemical interactions in solution, and chemical weathering. Agreement between observed and simulated soil metal pools and surface water concentrations for recent years was generally satisfactory, the results confirming that most contemporary soil metal is from atmospheric pollution. Metals in catchments with organic-rich soils show some mobility, especially under more acid conditions, but the calcareous mineral soils have retained nearly all anthropogenic metal inputs. Complexation by dissolved organic matter and co-transport accounts for up to 80% of the Cu in surface waters.     

Kinetic extractions to assess mobilization of Zn, Pb, Cu, and Cd in a metal-contaminated soil: EDTA vs. citrate

Kinetic EDTA and citrate extractions were used to mimic metal mobilization in a soil contaminated by metallurgical fallout. Modeling of metal removal rates vs. time distinguished two metal pools: readily labile (QM1) and less labile (QM2). In citrate extractions, total extractability (QM1+QM2) of Zn and Cd was proportionally higher than for Pb and Cu. Proportions of Pb and Cu extracted with EDTA were three times higher than when using citrate. We observed similar QM1/QM2 ratios for Zn and Cu regardless of the extractant, suggesting comparable binding energies to soil constituents. However, for Pb and Cd, more heterogeneous binding energies were hypothesized to explain different kinetic extraction behaviors. Proportions of citrate-labile metals were found consistent with their short-term, in-situ mobility assessed in the studied soil, i.e., metal amount released in the soil solution or extracted by cultivated plants. Kinetic EDTA extractions were hypothesized to be more predictive for long-term metal migration with depth.