Nitrogen transformations in copper-contaminated soils and effects of lime and compost application on soil resiliency

 A neutral and an acidic soil were treated with different doses (0–3,000 mg Cu kg^–1 soil as CuSO₄) of copper. The percentages of inhibition of nitrification in both soils varied from 5 to 97%, but for the N mineralization these percentages varied from 8 to 65%. The toxic effect of Cu for basal nitrification and N mineralization was assessed as critical. Nitrification was more sensitive than ammonification to copper toxicity. It appears that an ecological dose of inhibition for nitrification and N mineralization higher than 10% is suitable as an indicator for Cu contamination. Soil resiliency assessed by N mineralization in the lime treatments varied from 11 to 154% in the sandy soil and from 70 to 168% in the sandy loam soil. A combined application of lime and compost significantly increased soil resiliency. The percentage increase varied from 904 to 1,390% in the sandy soil and from 767 to 2,230% in the sandy loam soil. It appears that compost was a powerful agent for recovering the soil fertility of Cu-contaminated soils as assessed by N transformation. The acidic sandy soil showed a lower capacity for recovery after Cu toxicity stress. Received: 27 February 1999     

Crop contamination by selected trace elements

Goal and Background  The regulatory limit for the allowable concentration of heavy metals (HM) in agricultural soils should be based both on HM status and on soil parameters that influence HM mobility. In this paper, a soil categorization scheme is proposed which is based on the main factors that influence HM mobility in soils. The scheme also makes use of the existing regulatory limits for total concentrations of trace elements in Slovak soils but additionally takes into account the potential ability of the soils to mobilize trace elements. A map of the Slovak Republic showing the soil categorization using this scheme is presented. Methods  Besides total soil content of Cd, Pb, Cr, Hg, As, Cu, Zn, Ni, soil parameters with dominant influence on HM mobility are included in the scheme pH, organic matter content, quality of humus represented by spectral parameter Q⁴ ₆ and content of fraction f < 0.01 mm. Point rating approach was used for categorization. Database of localized soil data from 3556 locations was used for creation of map in GIS environment. Results  Based on the point scoring method described herein, soils are ranked from a (the least risk of crop contamination) to d (medium risk). Categories e and f are reserved for soils where the risk exceeds the allowable regulatory limits. For each of the six categories, the most suitable usage of agricultural land is recommended. The Slovak map presented shows that the main factor that affect the spatial distribution of each soil category is soil parent material which governs the existing total HM content and the predisposition for certain soil types to have high HM mobility. Agricultural usage of land in Slovakia is in most cases limited by exceedences of Cr and Ni, originating from widespread flysch rock parent material. Conclusions  Application to regional geochemical data shows that, for more than half of Slovak agricultural land, risk of crop contamination is low. For the rest of the area, planting should consider sensitivity of crops to HM uptake. Recommendation and Outlook  Evaluation of suitable agricultural usage based on HM contamination risk, should include not only the total HM content but also the potential for HM mobility, which can increase the risk of plant contamination. Where HM mobility data are not available, soil parameter data that influence HM mobility can be used to predict the potential HM soil contamination hazard.     

The effect of model soil contamination with Cr,Cu, Ni,and Pb on the biological properties of soils in the dry steppe and semidesert regions of southern Russia

Model soil contamination with Cr, Cu, Ni, and Pb in the dry steppes and semideserts of southern Russia has worsened the biological soil properties. With respect to the degree of deterioration of the biological properties, the soils can be arranged in the following sequence: dark chestnut soils > chestnut soils > light chestnut soils > brown semidesert soils > sandy brown semidesert soils. The sequence of metal oxides according to the adverse effect on the biological soil properties is as follows: CrO₃ > CuO ≥ PbO ≥ NiO.     

Effect of heavy metals contamination on root-derived and organic matter-derived CO2 efflux from soil planted with Zea mays

The CO₂ efflux from loamy Haplic Luvisol and heavy metal (HM) uptake by Zea mays L. were studied under increased HM contamination: Cd, Cu, and Ni up to 20, 1000, and 2500 mg kg⁻¹ soil, respectively. Split-root system with contrasting HM concentrations in both soil halves was used to investigate root-mediated HM translocation in uncontaminated soil zones. To separate root-derived and soil organic matter (SOM)-derived CO₂ efflux from soil, ¹⁴CO₂ pulse labeling of 15-, 25-, and 35-days-old plants was applied. The CO₂ evolution from the bare soil was 10.6 μg C–CO₂ d⁻¹ g⁻¹ (32 kg C–CO₂ d⁻¹ ha⁻¹) and was not affected by HM (except 2500 mg Ni kg⁻¹). The average CO₂ efflux from the soil with maize was about two times higher and amounted for about 22.0 μg C–CO₂ d⁻¹ g⁻¹. Portion of assimilates respired in the rhizosphere decreased with plant development from 6.0 to 7.0% of assimilated C for 25-days-old Zea mays to 0.4–2.0% for 45-days-old maize. The effect of the HM on root-derived ¹⁴CO₂ efflux increased with rising HM content in the following order: Cd < Cu < Ni. In Cu and Ni contaminated soils, shoot and root dry matter decreased to 70% and to 50% of the uncontaminated control, respectively. Plants contained much more HM in the roots than in the shoots. A split-root system with contrasting HM concentrations allowed to trace transport of mobile forms of HM by roots from contaminated soil half into the uncontaminated soil half. The portion of mobile HM forms in the soil (1 M NH₄NO₃ extract) increased with contamination and amounted to 9–16%, 2–6% and 1.5–3.5% for Cd, Cu, and Ni, respectively. Corresponding values for the easily available HM (1 M NH₄OAc extract) were 22–52%, 1–20% and 5–8.5%. Heavy metal availability for plants decreased in the following order: Cd > Cu ≥ Ni. No increase of HM availability in the soil was found after maize cultivation.     

Carbon and trace element fluxes in the pore water of an urban soil following greenwaste compost, woody and biochar amendments, inoculated with the earthworm Lumbricus terrestris

The benefits of adding composted organic materials to soils to enhance carbon storage could be countered by the mobilisation of some harmful pollutants commonly found in frequently degraded urban soils. Therefore non-composted materials could be a safer option. In the present study, carbon and trace element fluxes in soil pore water were studied in response to the surface mulch addition and the incorporation into an urban soil of greenwaste compost versus two non-composted amendments; a woody oversize material and biochar following inoculation with the vertical burrowing earthworm Lumbricus terrestris. The aim was to establish (i) to what extent the non-composted amendments impacted on mobility of soluble trace elements in the soil, compared to the composted amendment, and (ii) if/how this was regulated by earthworm activity.Both composted and non-composted amendments enhanced dissolved organic carbon (DOC) in soil pore water to ∼100-300 mg l⁻¹ in the upper depth of the soil profile above which they were applied as a mulch and similarly within the mesocosms in which they were mixed. Dissolved organic carbon, dissolved nitrogen (DTN) and trace metals, especially Cu and Pb, where enhanced to the greatest extent by greenwaste compost, because of strong co-mobilisation of metals by DOC. Biochar enhanced As and Cu mobility in the field profile and, additionally Pb in the mesocosms, with no effect on Cd. The woody, oversize amendment neither greatly increased DOC nor As, Cu, Pb or Zn mobility although, unlike the other amendments, earthworms increased DOC and Cd mobility when soils were amended with this material.This study concludes that non-composted amendments had a lower impact on DOC and thus trace element co-mobility than the composted greenwaste in this urban soil, whilst the general influence of earthworms was to reduce DOC and hence associated trace element mobility. In wider environmental terms the addition of non-composted materials to some urban soils, versus composted greenwaste could reduce the risk of mobilising potentially harmful elements, whilst usefully improving soil quality.     

Plant Availability and Uptake of Lead, Zinc, and Cadmium in Soils Contaminated with Anti-corrosion Paint from Pylons in Comparison to Heavy Metal Contaminated Urban Soils

Red lead (Pb₃O₄) has been used extensively in the past as an anti-corrosion paint for the protection of steel constructions. Prominent examples being some of the 200,000 high-voltage pylons in Germany which have been treated with red lead anti-corrosion paints until about 1970. Through weathering and maintenance work, paint compounds and particles are deposited on the soils beneath these constructions. In the present study, six such “pylon soils” were investigated in order to characterize the plant availability and plant uptake of Pb, Cd, and Zn. For comparison, three urban soils with similar levels of heavy metal contamination were included. One phase extractions with 1 M NH₄NO₃, sequential extractions (seven steps), and extractions at different soil pH were used to evaluate the heavy metal binding forms in the soil and availability to plants. Greenhouse experiments were conducted to determine heavy metal uptake by Lolium multiflorum and Lactuca sativa var. crispa in untreated and limed red lead paint contaminated soils. Concentrations of Pb and Zn in the pylon soils were elevated with maximum values of 783 mg Pb kg⁻¹ and 635 Zn mg kg⁻¹ while the soil Cd content was similar to nearby reference soils. The pylon soils were characterized by exceptionally high proportions of NH₄NO₃-extractable Pb reaching up to 17% of total Pb. Even if the relatively low pH of the soils is considered (pH 4.3–4.9), this appears to be a specific feature of the red lead contamination since similarly contaminated urban soils have to be acidified to pH 2.5 to achieve a similarly high Pb extractability. The Pb content in L. multiflorum shoots reached maximum values of 73 mg kg⁻¹ after a cultivation time of 4 weeks in pylon soil. Lime amendment reduced the plant uptake of Pb and Zn significantly by up to 91%. But L. sativa var. crispa cultivated on soils limed to neutral pH still contained critical Pb concentrations (up to 0.6 mg kg⁻¹ fresh weight). Possible mechanisms for the exceptionally high plant availability of soil Pb derived from red lead paint are discussed.     

Characterization of soil heavy metal pools in paddy fields in Taiwan: chemical extraction and solid-solution partitioning

Background, aim, and scope  Ongoing industrialization has resulted in an accumulation of metals like Cd, Cu, Cr, Ni, Zn, and Pb in paddy fields across Southeast Asia. Risks of metals in soils depend on soil properties and the availability of metals in soil. At present, however, limited information is available on how to measure or predict the directly available fraction of metals in paddy soils. Here, the distribution of Cd, Cu, Cr, Ni, Zn, and Pb in 19 paddy fields among the total, reactive, and directly available pools was measured using recently developed concepts for aerated soils. Solid-solution partitioning models have been derived to predict the directly available metal pool. Such models are proven to be useful for risk assessment and to derive soil quality standards for aerated soils. Material and methods  Soil samples (0–25 cm) were taken from 19 paddy fields from five different communities in Taiwan in 2005 and 2006. Each field was subdivided into 60 to 108 plots resulting in a database of approximately 3,200 individual soil samples. Total (Aqua Regia (AR)), reactive (0.43 M HNO₃, 0.1 M HCl, and 0.05 M EDTA), and directly available metal pools (0.01 M CaCl₂) were determined. Solid-solution partitioning models were derived by multiple linear regressions using an extended Freundlich equation using the reactive metal pool, pH, and the cation exchange capacity (CEC). The influence of Zn on metal partitioning and differences between both sampling events (May/November) were evaluated. Results  Total metals contents range from background levels to levels in excess of current soil quality standards for arable land. Between 3% (Cr) and 30% (Cd) of all samples exceed present soil quality standards based on extraction with AR. Total metal levels decreased with an increasing distance from the irrigation water inlet. The reactive metal pool relative to the total metal content is increased in the order Cr << Ni = Zn < Pb < Cu < Cd and ranged from less than 10% for Cr to more than 70% for Cd. Despite frequent redox cycles, Cd, Pb, and Cu appear to remain rather reactive. The methods to determine the reactive metal pool in soils yield comparable results, although the 0.43 M HNO₃ extraction is slightly stronger than HCl and EDTA. The close correlation between these methods suggests that they release similar fractions from soils, probably those reversibly sorbed to soil organic matter (SOM) and clay. The average directly available pool ranged from less than 1% for Cu, Pb, and Cr to 10% for Ni, Zn, and Cd when compared to the reactive metal pool. For Cd, Ni, Zn, and to a lesser extent for Cu and Pb, solid-solution partitioning models were able to explain up to 93% (Cd) of the observed variation in the directly available metal pool. CaCl₂ extractable Zn increased the directly available pool for Ni, Cd, and Cu but not that of Pb and Cr. In the polluted soils, the directly available pool was higher in November compared to that in May. Differences in temperature, rainfall, and changes in soil properties such as pH are likely to contribute to the differences observed within the year. The solid-solution partitioning model failed to explain the variation in the directly available Cr pool, probably because Cr is present in precipitates rather than being adsorbed onto SOM and clay. Despite obvious differences in parent material, source of pollution, climate, and land use, solid-solution partitioning of Cd in paddy fields studied here was similar to that in soils from Belgium and the Netherlands. Discussion  To assess risks of metals in soils, both analytical procedures as well as models are needed. The three methods tested here to determine the reactive metal pool are highly correlated and either of these can be used. The directly available pool was predicted most accurately by the 0.43 M HNO₃ method. The similarity of metal partitioning in paddy soils compared to well-drained soils suggests that changing redox conditions in paddy fields have a limited effect on the geochemical behavior of metals like Cd, Ni, and Zn. Small but significant differences in the directly available metal pool during the year suggest that redox cycles as well as differences in rainfall and temperature affect the size of the directly available metal pool. The large observed spatial heterogeneity of contaminant levels requires ample attention in the setup of soil monitoring programs. Conclusions  The directly available pool (0.01 M CaCl₂) of Cd, Zn, and Ni in paddy fields can be described well by an extended Freundlich model. For Cu and Pb, more information on dissolved organic carbon is needed to obtain a more accurate estimate of the directly available pool. Recommendations and perspectives  Soil testing protocols and models used in risk assessment consider the availability of pollutants rather than the total metal content. Results from extensive testing indicate that approaches developed for nontropical regions can be applied in paddy fields as well for metals like Cd, Ni, and Zn. This study shows that the chemical behavior under drained conditions in paddy fields is comparable to that observed in soils across the European Union, which allows regions with large scale soil pollution including Taiwan to apply such concepts to derive meaningful experimental protocols and models to assess risks of metals in soils.     

Desorption behaviour of lead in two calcareous soils as affected by Pb level without and with compost supply

A laboratory study was performed to investigate the influence of soil texture (sandy loam vs. clay loam), Pb supply (as Pb(NO₃)₂ without or with compost) and Pb levels on the extraction of available Pb by diethylene triamine pentaacetic acid (DTPA) and its desorption patterns at ten shaking periods. The soils were polluted with five Pb levels without or with compost and incubated for 1 month. Kinetic models commonly used to study the release of the nutrients were used in this study. Results showed that Power function model described the pattern of Pb desorption better than other models. The amount of extracted Pb increased as the Pb levels increased and was found to be higher in sandy loam soil treated with Pb without compost than that of clay loam soil treated with Pb with compost. The a value (Pb desorption constant) was the highest in sandy loam soil amended with Pb without compost. The lowest value of a, however, was observed in clay loam soil amended with Pb with compost. The ab coefficient (initial desorption rate of Pb) was higher in sandy loam than clay loam soil, demonstrating higher initial release rates of Pb in the coarser-textured soil. Addition of Pb without compost resulted in a higher increase in ab value in comparison with Pb with compost, in both the soils.     

Effect of low‐temperature biochar derived from pig manure and poultry litter on mobile and organic matter‐bound forms of Cu,Cd, Pb and Zn in sandy soil

Numerous studies conducted so far have shown that biochar has a significant effect on physical, chemical and biological properties of soils. Biochar can be used to alleviate the effects of soil contamination with organic and inorganic compounds, for instance, to reduce the mobility of heavy metals. The aim of the research was to evaluate the effect of pig manure and poultry litter, as well as biochars produced from these materials at a temperature of 300 °C on Cu, Cd, Pb and Zn contents in mobile and organic matter‐bound forms in soil. The research was conducted under laboratory conditions. The materials were introduced into sandy acid soil in doses of 0.5, 1.0 and 2.0% w/w. The application of pig manure‐derived biochar (BPM) and poultry litter‐derived biochar (BPL), depending on the amount added, reduced the mobility of copper from 28 to 69%, from 77 to 100% in the case of cadmium, from 94 to 99% in the case of lead, and from 15 to 97% in the case of zinc. The 2% amendment of pig manure (PM) and poultry litter (PL) caused an increase in the content of Cu extracted with NH₄NO₃ in comparison with the control treatment. A similar situation was observed in the case of zinc after the application of 0.5 and 1% amendments of pig manure (PM). Cu, Cd, Pb and Zn contents extracted with 0.025 mol C₁₀H₂₂N₄O₈ were higher than contents of these elements extracted with 1 m NH₄NO₃, mainly due to different extraction force of the extractants. The obtained results indicate that, compared with the content determined in soil from the control treatment, 1 and 2% amendments of both unconverted and thermally converted materials to the soil had a greater effect on contents of Cu, Pb and Zn in the organic matter‐bound fraction than the 0.5% amendment. The organic materials applied did not affect the content of cadmium in organic matter‐bound fraction.     

Heavy metal distribution in different soil aggregate size classes from restored brackish marsh,oil exploitation zone,and tidal mud flat of the Yellow River Delta

Purpose

Heavy metal distribution in soils is affected by soil aggregate fractionation. This study aimed to demons trate the aggregate-associated heavy metal concentrations and fractionations in “sandy,” “normal,” and “mud” soils from the restored brackish tidal marsh, oil exploitation zone, and tidal mudflat of the Yellow River Delta (YRD), China.

Materials and methods

Soil samples were sieved into the aggregates of >2, 0.25–2, 0.053–0.25, and <0.053 mm to determine the concentrations of exchangeable (F1), carbonate-bound (F2), reducible (F3), organic-bound (F4), and residual fraction (F5) of Cd, Cr, Cu, Ni, Pb, and Zn.

Results and discussion

The 0.25–2 mm aggregates presented the highest concentrations but the lowest mass loadings (4.23–12.18 %) for most metal fractions due to low percentages of 0.25–2 mm aggregates (1.85–3.12 %) in soils. Aggregates <0.053 mm took majority mass loadings of metals in sandy and normal soils (62.04–86.95 %). Most soil aggregates had residual Cr, Cu, Ni, Zn, and reducible Cd, Pb dominated in the total Cd, Cr, Cu, Ni, Pb, and Zn concentrations. Sandy soil contained relatively high F4, especially of Cu (F4) in 0.25–2 mm aggregates (10.22 mg kg^?1), which may relate to significantly high organic carbon contents (23.92 g kg^?1, P?<?0.05). Normal soil had the highest total concentrations of metals, especially of Cu, Ni, and Pb, which was attributed to the high F3 and F5 in the <0.053 mm aggregates. Although mud soil showed low total concentrations of heavy metals, the relatively high concentrations of bioavailable Cd and Cu resulted from the relatively high Cd (F2) and Cu (F2) in the >2 mm aggregates indicated contribution of carbonates to soil aggregation and metal adsorption in tidal mud flat.

Conclusions

Soil type and aggregate distribution were important factors controlling heavy metal concentration and fractionation in YRD wetland soil. Compared with mud soil, normal soil contained increased concentrations of F5 and F3 of metals in the 0.053–0.25 mm aggregate, and sandy soil contained increased concentrations of bioavailable and total Cr, Ni, and Zn with great contribution of mass loadings in the <0.053 mm aggregate. The results of this study suggested that oil exploitation and wetland restoration activities may influence the retention characteristics of heavy metals in tidal soils through variation of soil type and aggregate fractions.

     

Effects of a humic deposit (gyttja) on soil chemical and microbiological properties and heavy metal availability

The influence of a humic deposit (Gyttja, G) alone (applied at 25 kg ha⁻¹) and in combination with mineral fertilizer (G + NP) on soil organic matter content, pH, electrical conductivity, total N content, calcium carbonate content, enzyme activities (urease, β-glucosidase, arylsulphatase, and alkaline phosphatase), microbial biomass C, soil respiration, and availability of Cd, Pb, Ni, and Zn was examined through a 180-day incubation period and compared with the behavior of no treatment (control) and NP treatment. A significant increase in organic matter content was observed in soils treated with G + NP. Compared with G and NP alone, the G + NP-amended soils showed higher values of the selected microbiological properties.Diethylenetriaminepentaacetic-acid-extractable Cd, Pb, Ni, Cu, and Zn increased significantly with increasing rates of NP, but the addition of G + NP resulted in a considerable decrease in the amount of extractable metals during the incubation period (P<0.05). Based on these results, it can be concluded that the organic matter applied in the gyttja led to an increase in the metal adsorption capacity of the amended soils. This material can be used to reduce the availability and mobility of heavy metals in the soils intensively amended with mineral fertilizers. A combination of G with NP can, therefore, be considered as an alternative approach in the applications of organomineral fertilization.     

Microbial and enzyme properties of apple orchard soil as affected by long-term application of copper fungicide

Copper-based fungicides have been applied in apple orchards for a long time, which has resulted in increasing soil Cu concentration. However, the microbial and enzyme properties of the orchard soils remain poorly understood. This study aimed to evaluate the effect of long-term application of Cu-based fungicides on soil microbial (microbial biomass carbon (C_mic), C mineralization, and specific respiration rate) and enzyme (urease, acid phosphatase, and invertase activities) properties in apple orchards. Soil samples studied were collected from apple orchards 5, 15, 20, 30, and 45 years old, and one adjacent forest soil as for reference. The mean Cu concentrations of orchard soils significantly increased with increasing orchard ages ranging from 21.8 to 141 mg kg⁻¹, and the CaCl₂-extractable soil Cu concentrations varied from 0.00 to 4.26 mg kg⁻¹. The soil mean C_mic values varied from 43.6 to 116 mg kg⁻¹ in the orchard soils, and were lower than the value of the reference soil (144 mg kg⁻¹). The ratio of soil C_mic to total organic C (C_org) increased from 8.10 to 18.3 mg C_mic g⁻¹ C_org with decreasing orchard ages, and was 26.1 mg C_mic g⁻¹ C_org for the reference soil. A significant correlation was observed between total- or CaCl₂-extractable soil Cu and soil C_mic or C_mic/C_org, suggesting that the soil Cu was responsible for the significant reductions in C_mic and C_mic/C_org. The three enzyme activity assays also showed the similar phenomena, and declined with the increasing orchard ages. The mean soil C mineralization rates were elevated from 110 to 150 mg CO₂-C kg⁻¹ soil d⁻¹ compared with the reference soil (80 mg CO₂-C kg⁻¹ soil d⁻¹), and the mean specific respiration rate of the reference soil (0.63 mg CO₂-C mg⁻¹ biomass C d⁻¹) was significantly smaller than the orchard soils from 1.19 to 3.55 mg CO₂-C mg⁻¹ biomass C d⁻¹. The soil C mineralization rate and the specific respiration rate can be well explained by the CaCl₂-extractable soil Cu. Thus, the long-term application of copper-based fungicides has shown adverse effects on soil microbial and enzyme properties.     

Protozoan bioassays of soil amended with sewage sludge and heavy metals,using the common soil ciliate Colpoda steinii

The common soil protozoan Colpoda steinii was used to study the toxicity of sulphate solutions of Ni, Cd, Cu, and Zn. The growth of C. steinii was reduced by 50% in the presence of 0.10, 0.22, 0.25, and 0.85 mg litre^-1 of Ni, Cd, Cu and Zn, respectively, during 24 h of incubation at 25°C, as calculated from a regression analysis of probit-transformed data. The same growth assay was used to assess the toxicity of soil solution extracted by centrifugation from soil samples of field plots of a grass/clover ley on a sandy loam treated with sewage sludge spiked with additional Cd, Cu, Cr, Ni, Pb, or Zn at concentrations either equivalent to or twice the limits for heavy metals recommended in recent EC guidelines (Commission of European Communities directive 86/278/EEC). The toxicity of these soil solutions varied with the season of the year. None of the soil solutions extracted in winter (February 1991) inhibited the growth of C. steinii. In summer (July 1991), the growth was reduced in solutions extracted from plots that were amended with sludge plus additional Zn or Ni at twice the maxima recommended by the EC. The changes in toxicity to C. steinii of the soil solutions between February and July were positively correlated with increases in heavy metal concentrations of Zn and Ni between winter and summer. These preliminary results suggest that regular protozoan bioassays may be used to monitor the biological availability of heavy metals in soils, especially when combined with other microbial assays and with chemical analyses of soil solutions.     

Heavy metals in the soil–plant system of the Don River estuarine region and the Taganrog Bay coast

Purpose

The aim of this work was to study the level and degree of mobility of heavy metals in the soil–plant system and to perform bioindication observations in the Don River estuarine region and the Russian sector of the Taganrog Bay coast.

Materials and methods

The objects of the study included samples of zonal soils (chernozem) and intrazonal soils (alluvial meadow and alluvial-stratified soils, Solonchak, sandy primitive soil) from monitoring stations of the Don river estuarine region and the Taganrog Bay coast, as well as their higher plants: Phragmites australis Cav., Typha angustifolia L., Carex riparia Curtis, Cichorium intybus L., Bolboschoenus maritimus L. Palla, and Rumex confertus Willd. The total concentrations of Mn, Ni, Cd, Cu, Zn, Pb, and Cr in the soils were determined by X-ray fluorescent scanning spectrometer. The concentration of heavy metal mobile forms exchangeable, complex compounds, and acid-soluble metal were extracted using the following reagents: 1 N NH₄Ac, pH 4.8; 1 % EDTA in NH₄Ac, pH 4.8; 1 N HCl, respectively. Heavy metals in plants were prepared for analysis by dry combustion at 450 °C. The heavy metal concentration in extracts from plants and soils was determined by AAS.

Results and discussion

The total contents of heavy metals in the soil may be described with a successively decreasing series: Mn?>?Cr?>?Zn?>?Ni?>?Cu?>?Pb?>?As?>?Cd. The total concentrations of As, Cd, and Zn in the soil exceed the maximum permissible concentrations levels. Contamination of alluvial soils in the estuarine zone with mobile Сu, Zn, Pb, and Cd has been revealed, which is confirmed by the high bioavailability of Cu and Zn and, to a lesser degree, Cd and Pb accumulating in the tissues of macrophytic plants. Data on the translocation of elements to plant organs have showed their predominant accumulation in the roots. Bioindication by the morphofunctional parameters of macrophytic plants (with a Typha L. species as an example) can be used for revealing the existence of impact zones with elevated contents of metals in aquatic ecosystems.

Conclusions

The results revealed that increased content of Zn, Pb, Cu, Ni, and As in soil have anthropogenic sources. The high content of Cr in the soils is related to the lithogenic factor and, hence, has a natural source.

     

Road-deposited sediment, soil and precipitation (RDS) in Bratislava, Slovakia: compositional and spatial assessment of contamination

Background, aim and scope  The urban environment in Bratislava is, in association with rapid urbanisation and industrialisation, significantly influenced by several potential sources of pollution, including automobile exhaust and industry emmissions. Urban road-deposited sediments contain many potentially toxic elements such as Pb, Cr, Cu, Zn and also Fe at concentrations much higher than in soil. In this study, the chemical composition and spatial variability of road-deposited sediments in urban area of Bratislava were assessed for the elements As, Cd, Cr, Cu, Hg, Ni, Pb, Fe and Mn. Additional evaluation of archive data for soil, snow and atmospheric dust was undertaken to provide an integrated view on urban environment contamination. Materials and methods  Urban road-deposited sediments (RDS) were collected during summer 2003 and 2004 mainly from major city crossroads. RDS samples were analysed for total metal content, pseudo-total metal content (HNO₃ digestion) and by a sequential extraction method, grain fraction composition and mineralogical composition (X-ray analysis). Metal concentrations in soil and snow samples from urban and non urban city area were compared. Results and discussion  The highest concentrations for all metals were found in the finest RDS fraction (<0.125 mm). Whilst in the fraction <1 mm mean concentrations of Cr, Cu and Pb reached 55.2, 143.8 and 34.4 mg kg⁻¹, respectively, for the fraction <0.125 mm, markedly higher contents of these elements were documented at the level of 86.8, 218.4 and 63.1 mg kg⁻¹, respectively. The soil contents of potentially toxic risk elements in the urban area including As, Cr, Cu, Fe, Hg, Mn, Ni, Pb and Zn were higher than in the non-urban area (except for Cd with similar contents). This distribution pattern of evaluated chemicals in urban and non-urban area is more evident in the case of winter precipitation (snow). The snow concentrations of As, Cr, Cu, Fe, Mn, Pb and Zn in the urban area were two tot five times higher than in non-urban area. Conclusions and recommendations  Monitoring of road-deposited sediments, dust, soil and precipitation has confirmed the significant contamination of the urban environment in Bratislava with potentially toxic elements that can pose a threat for the health of its residents. Future works should be based on analyses of temporal variability of RDS and analyses of organic matter content.     

Heavy metal accumulation and mobility in a soil profile depend on the organic waste type applied

Purpose

While organic waste amendments can initially improve soil physicochemical properties, including nutritional benefits to plants and increased microorganism activity, long-term application of excessive amounts of organic wastes can cause accumulation of heavy metals (HMs). Thus, the current study examined the accumulation of HMs in agricultural soil profiles following organic waste application.

Materials and methods

Three common organic sludge, including municipal sewage sludge (MSS), industrial sewage sludge (ISS), and leather sludge (LS), were applied annually to an agricultural soil under field conditions over 7 years (1994–2000) at a rate of 25 and 50 t ha^?1 year^?1. Subsequently, when organic sludge amendments were ceased, the experimental plots were cultivated without any treatments for another 12 years (2001–2012) and the changes in HM concentrations along the soil depth profile were monitored together with soil pH, dissolved organic carbon (DOC), and dehydrogenase activity (DHA).

Results and discussion

Significant increases in Cu, Pb, and Zn concentrations were observed down to a depth of 80 cm in soils treated with ISS and LS, where sludge application also increased the levels of Cd, Cr, Pb, and Zn and their movement down the soil profile. However, with the exception of Cu, no significant changes in HM concentrations were observed following treatment with MSS. At a depth of 80 cm, soils which had received 25 and 50 t ha^?1 LS showed, respectively, 4 and 14 times higher Cr levels than the control soil.

Conclusions

Organic sludge induced changes in soil pH and soil DOC concentration which were the key factors influencing HM movement and accumulation following organic sludge treatment.

     

Combined effects of soil waterlogging and compaction on rice (Oryza sativa L.) growth, soil aeration, soil N transformations and 15N discrimination

 The combined effects of soil compaction and soil waterlogging on the growth of two rice cultivars (Oryza sativa L., cultivars Kanto 168 and Koshihikari) and soil N transformations were studied in pots. Although waterlogging eliminated initial differences in mechanical resistance between compacted and loose soils, Kanto 168 and Koshihikari roots had, respectively, less biomass and a lower porosity if soil was compacted prior to waterlogging. The cause for this was probably established before waterlogging. Redox values showed that upland soils were well aerated. Loose waterlogged soils contained oxic sites, but compacted waterlogged soils did not. Potential denitrification was stimulated by waterlogging and, to a larger extent, by plant presence. Waterlogging lowered potential nitrifying capacities, by competition between plants and micro-organisms for NH₄ ⁺ rather than by oxygen shortage. Compaction prior to waterlogging benefited the potential nitrifying capacity of soils with either cultivar and the potential denitrifying capacity for soils with Koshihikari. Compaction had no effect on nitrification or denitrification in upland soils. N recoveries were low, especially in pots without plants, as a result from sampling strategy and N loss. On day 42/43 after potting, total δ¹⁵N values of waterlogged pots were positive, whereas after 22 days all pots had negative total δ¹⁵N values. Final δ¹⁵N values of plant parts from waterlogged and upland soils were positive and negative, respectively. Although the δ¹⁵N values generally accorded well with the other results, they did not support higher N losses from compacted waterlogged soils than from loose waterlogged soils with plants, as suggested by potential denitrifying activities. Received: 4 February 2000     

Multivariate geostatistical analysis of heavy metals in topsoils from Beijing,China

Background  Regional soil environmental quality is a hotspot and difficulty in the environmental sciences for the spatial variability of pollutants and the relationship between them. Beijing, the capital of China, has been undergoing a rapid economical development during the past three decades, and thus might encounter the same issues as the developed countries. However, there is little information about the soil environmental quality of Beijing, especially at the regional scale. The real soil environmental situation of heavy metals remains unknown, even less the sources of possible pollutants. Objectives  The main objectives were to identify the spatial variability and main sources of heavy metals in Beijing soils by conducting multivariate statistical analyses, including geostatistical analysis assisted with GIS tools. These results will contribute to the establishment of the soil quality baseline and the management of regional environment. Materials and Methods  Seven hundred and seventy-three samples of topsoils (0–20 cm) were collected from all over Beijing, China. The samples were digested with HNO₃ and H₂O₂. The concentrations of Cr, Cu, Ni, Pb and Zn were analyzed with a FL-AAS and those of Cd with a GF-AAS. The concentrations of As were determined with AFS-2202. Principal component analysis (PCA) and partial correlation analysis (CA) were used and geostatistics was conducted for the data processing. Results  Concentrations of topsoil As, Cd, Cr, Cu, Ni, Pb and Zn in the Beijing area were measured and contour maps were constructed to describe the metals’ spatial distribution. Except for the background effect of the soils, anthropogenic factors made the soil heavy metal concentrations increase, especially in the center of the city. Combined with the PCA results, it was found that vehicle exhaust and smelters were the main sources of soil heavy metals. Pedogenic factors were also controlling the spatial features of metals. Discussion  Combined with the results of PCA, 7 heavy metals could be divided into 4 factors. F1 was the metals, i.e., Cu, Pb, Zn, mainly controlled by the human activities. Cr and Ni was in F2, Cd in F3 and As in F4. These 3 factors might be controlled by the soil parent materials. Concentrations of 7 heavy metals were comparable with the first level of environmental quality standard for soils of China and much lower than the second level of national standard for soils. Conclusion  The heavy metal concentrations in the topsoil of Beijing are mostly comparable with the background values, especially for As, Cr and Ni. In the city center of Beijing, Cu, Pb and Zn had a high concentration of distribution. The spatial features of As, Cr and Ni are mainly controlled by pedogenic factors, whereas Cd, Cu, Pb and Zn are controlled by anthropogenic and parent factors. Traffic and smelting contribute greatly to the increase of Pb, Zn and Cu in the soil, especially in the center of the city. Landfill may have also affected the soil quality around it. Recommendation  Different factors were controlled by parent materials, which might be related to the different soil minerals. Further research should be conducted in Beijing to elucidate the relationship between heavy metals and soil minerals. ESS-Submission Editor: Chengron Chen, PhD (c.chen@griffith.edu.au)     

Response of the sorption behavior of Cu,Cd, and Zn to different soil management

This study investigated the effect of different farming practices over long time periods on the sorption‐desorption behavior of Cu, Cd, and Zn in soils. Various amendments in a long‐term field experiment over 44 y altered the chemical and physical properties of the soil. Adsorption isotherms obtained from batch sorption experiments with Cu, Cd, and Zn were well described by Freundlich equations for adsorption and desorption. The data showed that Cu was adsorbed in high amounts, followed by Zn and Cd. In most treatments, Cd ions were more weakly sorbed than Cu or Zn. Generally, adsorption coefficients K_F increased among the investigated farming practices in the following order: sewage sludge ≤ fallow < inorganic fertilizer without N ≈ green manure < peat < Ca(NO₃)₂ < animal manure ≤ grassland/extensive pasture. The impact of different soil management on the sorption properties of agricultural soils for trace metals was quantified. Results demonstrated that the soil pH was the main factor controlling the behavior of heavy metals in soil altered through management. Furthermore, the constants K_F and n of isotherms obtained from the experiments significantly correlated with the amount of solid and water‐soluble organic carbon (WSOC) in the soils. Higher soil pH and higher contents of soil organic carbon led to higher adsorption. Carboxyl and carbonyl groups as well as WSOC significantly influenced the sorption behavior of heavy metals in soils with similar mineral soil constituents.     

Influence of long-term conservation tillage on soil and rhizosphere microorganisms

 In long-term field experiments on sandy loam and loamy sand soils, the influence of conservation and conventional tillage on soil and rhizosphere microorganisms was studied. Conservation tillage stimulated rhizosphere bacteria on winter wheat, winter barley, winter rye and maize in different soil layers. Particularly the populations of Agrobacterium spp. and Pseudomonas spp. were increased. On the sandy loam, N₂ fixation and nodulation of pea plants were significantly increased. No influence of different soil tillage was determined on the colonization of the rhizosphere by mycorrhiza and saprophytic fungi. Stubble residues infected with Gaeumanomyces graminis were infectious for a longer time on the soil surface than after incorporation into the soil. Received: 10 March 1998