Attempts to derive EC50 values for heavy metals from land-applied Cu-, Ni-, and Zn-spiked sewage sludge

We established a field trial to assess the impacts on soil biological properties of application of heavy metal-spiked sewage sludge, with the aim of determining toxicity threshold concentrations of heavy metals in soil. Plots were treated with sludges containing increasing concentrations of Cu, Ni and Zn in order to raise the metal concentrations in the soil by 0-200 mg Cu kg⁻¹, 0-60 mg Ni kg⁻¹ and 0-400 mg Zn kg⁻¹, and were then cultivated and sown in ryegrass-clover pasture and monitored annually for 6 years. All biological properties measured (soil basal respiration, microbial biomass C, and sulphatase enzyme activities), except phosphatase activity, increased in all plots over the duration of the experiment. Consequently, it was only possible to assess effects of heavy metals across time if, each year, all data for each metal were normalised by expressing them as percentages of the activities measured in an un-sludged control plot. When this was done, no significant effects of increasing heavy-metal concentrations on basal respiration, microbial biomass C or respiratory quotient (qCO₂) were observed, although total Cu and soil solution Cu were significantly negatively related to microbial biomass C when it was expressed as a proportion of soil total C. None of the properties measured were affected by increasing Ni concentrations. Phosphatase and sulphatase activities were significantly negatively related to increasing Zn concentrations, but not usually to increasing Cu unless they were expressed as a proportion of total C. A sigmoidal dose-response model was used to calculate EC₂₀ and EC₅₀ values using the normalised data, but generally, the model parameters had very large 95% confidence intervals and/or the fits to the model had small R² values. The factors primarily responsible for confounding these results were site and sample variations not accounted for by the normalisation process and the absence of any data points at metal concentrations beyond the calculated EC₅₀ values. In the few instances where reasonable EC₂₀ values could be calculated, they were relatively consistent across properties, e.g., EC₂₀ for total Zn and phosphatase (330 mg kg⁻¹), total Zn and sulphatase (310 mg kg⁻¹), and EC₂₀ for total Cu and sulphatase (140 mg kg⁻¹) and total Cu and microbial biomass C (140 mg kg⁻¹), when both sulphatase and microbial biomass C were expressed as a proportion of total C. Our results suggest that Cu and Zn at the upper concentrations used in this experiment were possibly having adverse effects on some soil biological properties. However, much higher metal concentrations will be needed to accurately calculate EC₂₀ and EC₅₀ and this may not be easily achievable without many applications of sewage sludge, even if the sludge is spiked with heavy metals.     

Uptake and bioaccumulation of heavy elements by two earthworm species from a smelter contaminated area in northern Kosovo

As, Cd, Cu, Pb, Sb and Zn concentrations were determined in two earthworm species (Allolobophora rosea and Nicodrilus caliginosus) from a mining and industrial area in northern Kosovo and compared with their contents in the bulk soil and the main soil fractions. Earthworm specimens were collected at fifteen sites located at different distances from a Pb–Zn smelter along a gradient of decreasing contamination. Individuals of A. rosea and N. caliginosus showed similar tissue levels of As, Cd, Cu, Pb, Sb and Zn, suggesting that earthworm species belonging to the same eco-physiological group have a similar propensity to uptake and bioaccumulate heavy elements. Cd, Pb, Sb and Zn concentrations in both earthworm species were positively correlated with the respective total soil contents and generally decreased with distance from the smelter. The bioaccumulation factor (BAF) revealed that Cd and Zn were the only elements bioaccumulated by earthworms. The rank order of BAF values for both species was as follows: Cd > > Zn > > Cu > As = Pb = Sb. The absorption of Cd, Pb, Sb and Zn by earthworms mostly depended on the extractable, reducible and oxidable soil fractions, suggesting that the intestine is likely the most important uptake route. The extractable soil fraction constantly influenced the uptake of these heavy elements, whereas the reducible fraction was important mainly for Pb and Zn. The water soluble fraction had an important role especially for the most mobile heavy elements such as Cd and Zn, suggesting that dermal uptake is not negligible. As a whole, the analytical data indicate that soil fractionation patterns influence the uptake of heavy elements by earthworms, and the extractable fraction is a good predictor of heavy element bioavailability to these invertebrates in soil.     

Determination of the Bioavailable Fraction of Cu and Zn in Soils Amended with Biosolids as Determined by Diffusive Gradients in Thin Films (DGT), BCR Sequential Extraction, and Ryegrass Plant

This study assessed the effect of biosolids applied at rates, 0, 30, 45, and 60?Mg?ha^?1 on the chemical associations and bioavailability of Cu and Zn in soils from an important agricultural zone of the Metropolitan Region in Central Chile. Three methods were used to determine the bioavailability of Cu and Zn in soils: ryegrass (Lolium perenne) plants, diffusive gradients in thin films (DGT) technique, and Community Bureau of Reference (BCR) sequential extraction. The DGT effective concentration (C _E) and sequential extract acid soluble fraction of the BCR extraction (most labile fraction of the soils, normally associated with bioavailability) were compared with total metal concentration in ryegrass plants as a means to compare the chemical and biological measures of bioavailability. Total Zn was higher in comparison to Cu for all treatments. Concentrations were within the limits set by the Chilean regulations for land-applied biosolids. Metals in the control soil were primarily found in the residual fraction of soils. Biosolids application generally decreased this fraction, with a subsequent increase observed mainly in the acid soluble fraction. The contents of Cu and Zn in ryegrass plants increased with increasing rates of biosolids. Comparison of the Cu and Zn content in ryegrass plants with C _E, showed a good correlation for Zn. However, the C _E for soil Cu was only related to plant Cu for some of the soils studied. Correlation between Zn in ryegrass plants and the labile fraction of Zn as measured by the sequential extraction was excellent, with correlation coefficients >0.9, while for Cu, correlation coefficients were lower.     

Effects of azoxystrobin,chlorothalonil, and ethoprophos on the reproduction of three terrestrial invertebrates using a natural Mediterranean soil

The potential terrestrial toxicity of three pesticides, azoxystrobin, chlorothalonil, and ethoprophos was evaluated using reproduction ecotoxicological tests with different non-target species: the collembolan Folsomia candida, the earthworm Eisenia andrei, and the enchytraeid Enchytraeus crypticus. All reproduction tests were performed with natural soil from a Mediterranean agricultural area (with no pesticide residues) in order to improve the relevance of laboratory data to field conditions. Controls were performed with natural and standard artificial soil (OECD 10% OM). The fungicide azoxystrobin showed the highest toxicity to earthworms (EC₅₀ = 42.0 mg a.i. kg⁻¹ dw soil). Collembolans were the most sensitive taxa in terms of sublethal effects of chlorothalonil with an EC₅₀ of 31.1 mg a.i. kg⁻¹ dw soil followed by the earthworms with an EC₅₀ of 40.9 mg a.i. kg⁻¹ dw soil. The insecticide ethoprophos was the most toxic to collembolans affecting their reproduction with an EC₅₀ of 0.027 mg a.i. kg⁻¹ dw soil. Enchytraeids were generally the least sensitive of the three species tested for long-term effects. Earthworms were not always the most sensitive species, emphasizing the need to increase the number of mandatory assays with key non-target organisms in the environmental risk assessment of pesticides.     

Relationships of soil properties with Mn and Zn distribution in acidic soils and their uptake by a barley crop

The extractability and solid-phase fractionation of manganese (Mn) and zinc (Zn) in acid-to-neutral agricultural soils from Central Spain was evaluated by sampling and analysing twenty-nine representative soils and by greenhouse cropping eleven of them with spring barley (Hordeum vulgare, L.). All soil samples were extracted with three chemical extractants commonly used for soil fertility evaluation (0.43 M HOAc, DTPA and Mehlich-3). The soil samples were also operationally determined in six steps with the following extractants: 1 M Mg(NO₃)₂ extractable (WSEX, water soluble plus exchangeable), 0.7 M NaOCl extractable (OC, organically complexed), 0.1 M NH₂OH·HCl extractable (MnOX, Mn-oxide), 0.2 M (NH₄)₂C₂O₄ + 0.2 M H₂C₂O₄ extractable (AFeOX, amorphous Fe-oxide), 0.2 M (NH₄)₂C₂O₄ + 0.2 M H₂C₂O₄ + 0.1 M ascorbic acid extractable (CFeOX, crystalline Fe-oxide), and HCl, HNO₃, and HF in mixture (RES, residual). Soil-extractable amounts for the three single extractants were highly correlated with each other for both metals. Distributions among metal fractions showed that Mn was mainly found in the MnOX fraction (30.9%, ranging from 13.0 to 51.2%), whereas Zn was predominantly found in the RES fraction (44.3%, ranging from 26.4 to 56.8%). The proportion of Mn fractions extracted from the soils was in the order as follows: CFeOX ≤ WSEX = OC ≤ AFeOX = RES < MnOX, whereas Zn was in the order: WSEX ≤ OC ≤ AFeOX < MnOX < CFeOX < RES. The soil properties that correlated best with the distribution of Mn and Zn forms in these soils were soil organic matter and pH. The “availability factor” values [AF = (WSEX + OC) 100 / total metal], were higher for Mn than for Zn in these soils. Plant metal concentrations (Y) and soil-extractable and sequential extracted fractions showed few significant correlations. However, it was possible to significantly predict the phytoavailability of Mn and Zn for barley using a series of empirical equations involving extractable metals, solid-phase fractions and soil properties as components. The R² values of the best-fit regression models ranging from 0.50 [Y-Zn = 19.3 + 6.32 (WSEX + OC)-Zn] to 0.92 [Y-Zn = 57.3 + 0.23 P − 8.56 pH + 20.6 DTPA-Zn].     

Assaying the effects of chemical ameliorants with earthworms and plants exposed to a heavily polluted metalliferous soil

The study examined the effects of chemical ameliorant additions (1% montmorillonite, 1% hydroxylapatite, or 1% ferrous oxide) on the availability of cadmium (Cd), copper (Cu), lead (Pb) and zinc (Zn) to the earthworm, Lumbricus rubellus, exposed for 4 weeks to a circumneutral heavily polluted soil (Cd = 220 μg g^–1; Cu = 35 μg g^–1; Pb = 6070 μg g^–1; Zn = 124500 μg g^–1) in 1:0–1:3 dilutions with a clean soil, under laboratory conditions. Soil type (i.e. the dilution series) had a strong influence on the 1 M ammonium acetate extractable metal fractions in soil and on worm-tissue concentrations of Cd, Pb and Zn. Soil treatments (i.e. amelioration) significantly reduced only the soil Zn extractable fraction; Zn concentrations in worms tended to be lower in amended soils. A second experiment, involving curly cress (Lepidium sativum), grown either directly in the serial soil dilutions with 5% ameliorant additions or in the water-extractable fractions of the soils, indicated that root growth is a more sensitive endpoint of metal availability than chlorophyll assays. It was concluded that: (i) chemical immobilization of metals is probably most effective in soils with low to moderate degrees of metal pollution; (ii) an integrated suite of bioassays incorporating different, ecologically relevant, taxa is to be recommended for monitoring metal bioavailabilities and biological effects.     

Verhalten von Schwermetallen in Böden. 2. Extraktion mobiler Schwermetalle mittels CaCl2 und NH4NO3

Behaviour of heavy metals in soils. 2. Extraction of mobile heavy metals with CaCl₂ and NH₄NO₃ 156 soil samples from arable fields, grassland and forest stands were analysed for the CaCl₂^? and NH₄NO₃^? extractable contents of Cd, Zn, Mn, Cu and Pb. The average amounts of Cd, Zn, Cu and Pb extracted with CaCl₂ are higher compared with NH₄NO₃ whereas the relation for Mn is vice versa. The proportion of the NH₄NO₃^? extractable contents in percent of the CaCl₂^? extractable contents of Cd, Zn and Pb decrease with increasing pH, whereas the contents of Mn and Cu increase. Inspite of a differing extraction behaviour of the two salt solutions the CaCl₂^? and NH₄NO₃^? extractable amounts of Cd, Mn, Zn und Pb are highly correlated and can be converted one into another. The mobile (CaCl₂, NH₄NO₃) proportion of the corresponding total, EDTA and DTPA heavy metal contents is in close relation to the pH of the soils. Using CaCl₂ solution the threshold pH values for an increasing mobility decrease in the order Cd > Mn > Zn > Cu > Pb, using NH₄NO₃ as extractant the order is Mn > Cd > Zn > Cu > Pb. In the case of CaCl₂ as extractant soluble chloro-Cd-complexes will be formed so that the Cd mobility in soils will be overestimated in most cases.     

Linkages between soil micro-site properties and CO2 and N2O emissions during a simulated thaw for a northern prairie Mollisol

Biologically derived emissions of carbon dioxide (CO₂) and nitrous oxide (N₂O) at 0 °C vary with soil depth during soil thawing. Micro-site soil properties, especially those which influence porosity and substrate availability, also vary with depth and may help explain gas emissions. Intact soil cores collected to a depth of 80 cm from an undisturbed prairie Mollisol in central North Dakota were uniformly subjected to distinct temperature steps during a simulated soil thaw (−15 to 5 °C) and sampled for CO₂ and N₂O emissions throughout the soil profile. Emission data were fit to a first order exponential equation (E = αe^βT). Cores were then analyzed in 10 cm depth increments for micro-site properties including root length and mass, aggregation, and organic substrate availability (available, aggregate-protected and mineral-bound pools). Both CO₂ and N₂O emissions at 0 °C declined exponentially with depth. Emissions of CO₂ and N₂O at 0 °C were strongly related to root length (R² = 0.80 and 0.76, respectively), root mass (R² = 0.56 and 0.74), large macroaggregate mass (R² = 0.63 and 0.54), and aggregate-protected organic matter (R² > 0.57), while available organic matter was related to CO₂ (R² > 0.60) and not N₂O. When CO₂ and N₂O emissions were normalized by available and aggregate-protected carbon pools, respectively, nutrient use efficiency increased significantly with depth. Results suggest CO₂ and N₂O emissions are (1) positively influenced by the rhizosphere and (2) differentially affected by substrate pool or location. CO₂ emissions were more positively affected by available substrate, while N₂O emissions were more positively affected by less labile, aggregate-protected substrate.     

Uptake and bioaccumulation of heavy elements by two earthworm species from a smelter contaminated area in northern Kosovo

As, Cd, Cu, Pb, Sb and Zn concentrations were determined in two earthworm species (Allolobophora rosea and Nicodrilus caliginosus) from a mining and industrial area in northern Kosovo and compared with their contents in the bulk soil and the main soil fractions. Earthworm specimens were collected at fifteen sites located at different distances from a Pb–Zn smelter along a gradient of decreasing contamination. Individuals of A. rosea and N. caliginosus showed similar tissue levels of As, Cd, Cu, Pb, Sb and Zn, suggesting that earthworm species belonging to the same eco-physiological group have a similar propensity to uptake and bioaccumulate heavy elements. Cd, Pb, Sb and Zn concentrations in both earthworm species were positively correlated with the respective total soil contents and generally decreased with distance from the smelter. The bioaccumulation factor (BAF) revealed that Cd and Zn were the only elements bioaccumulated by earthworms. The rank order of BAF values for both species was as follows: Cd > > Zn > > Cu > As = Pb = Sb. The absorption of Cd, Pb, Sb and Zn by earthworms mostly depended on the extractable, reducible and oxidable soil fractions, suggesting that the intestine is likely the most important uptake route. The extractable soil fraction constantly influenced the uptake of these heavy elements, whereas the reducible fraction was important mainly for Pb and Zn. The water soluble fraction had an important role especially for the most mobile heavy elements such as Cd and Zn, suggesting that dermal uptake is not negligible. As a whole, the analytical data indicate that soil fractionation patterns influence the uptake of heavy elements by earthworms, and the extractable fraction is a good predictor of heavy element bioavailability to these invertebrates in soil.     

Effects of salinity on partitioning, uptake and toxicity of zinc in the earthworm Eisenia fetida

Salinisation of soil is a problem in many parts of the world especially in agricultural lands that could also be contaminated with metals from pesticide use. This study aimed to derive a quality criterion standard in a defined substrate with the eventual aim of protecting earthworms against salinity, and to assess the influence of salinity on partitioning of, uptake in and toxicity of zinc to earthworms. To achieve this, two experiments were conducted with specimens of Eisenia fetida exposed in the laboratory for 28 days using OECD artificial soil spiked with either NaCl (experiment 1) or combination of Zn and NaCl (experiment 2). In the first experiment, NaCl was added in the following concentrations: 0, 1000, 2000, 4000, 6000 and 8000 mg kg⁻¹ NaCl. Mortality, growth and cocoon production were assessed at day 28. The results showed 28-day LC₅₀ of 5436 mg kg⁻¹ for NaCl. The EC₅₀s for growth and cocoon production were 4985 and 2020 mg kg⁻¹ NaCl, respectively. In the second experiment, Zn, added as ZnCl₂ in a range of sub-lethal concentrations (0, 250, 500, 750 mg kg⁻¹ Zn) was combined with 0, 2000 or 4000 mg kg⁻¹ NaCl. The endpoints: mortality, weight change, and the internal zinc concentration were assessed at day 1, 7, 14 and 28 while cocoon production was assessed only at day 28. Apart from the total zinc concentration in the substrates, DTPA and CaCl₂ extractable Zn concentrations were also determined at day 1 and 28 to assess how salinity influenced the partitioning of this metal in the substrates. There was a significant increase in CaCl₂ and DTPA extractable Zn in the substrates as salinity increased suggesting that salinity influenced the partitioning of Zn in the substrates. Weight and mortality of worms were not significantly affected by NaCl and Zn as individual substances, but in combination both had significant effects on these parameters. In contrast, cocoon production was significantly affected by increased NaCl and Zn administered as individual substances, and the effects were more severe when both substances were present. The apparent synergy between Zn and NaCl could not be fully explained by internal zinc concentrations in the worms. It could, however, be partly explained by Cl⁻ effect from the addition of Zn as ZnCl₂. It is concluded that salinity resulting from increased NaCl had an additive to synergistic effect in combination with Zn, in influencing toxicity to these earthworms.     

Soil classification provides a poor indicator of carbon turnover rates in soil

Most soil surveys are based on soil geomorphic, physical and chemical properties, while many classifications are based on morphological properties in soil profile. Typically, microbial properties of the soil (e.g. biomass and functional diversity) or soil biological quality indicators (SBQIs) are not directly considered in soil taxonomic keys, yet soil classification schemes are often used to infer soil biological function relating to policy (e.g. soil pollution attenuation, climate change mitigation). To critically address this, our aim was to assess whether rates of carbon turnover in a diverse range of UK soils (n > 500) could effectively be described and sub-divided according to broadly defined soil groups by conventional soil classification schemes. Carbon turnover in each soil over a 90 d period was assessed by monitoring the mineralisation of either a labile (¹⁴C-labelled artificial root exudates) or more recalcitrant C source (¹⁴C-labelled plant leaves) in soil held at field capacity at 10 °C. A double exponential first order kinetic model was then fitted to the mineralisation profile for each individual substrate and soil. ANOVA of the modelled rate constants and pool sizes revealed significant differences between soil groups; however, these differences were small regardless of substrate type. Principle component and cluster analysis further separated some soil groups; however, the definition of the class limits remained ambiguous. Exclusive reference values for each soil group could not be established since the model parameter ranges greatly overlapped. We conclude that conventional soil classification provides a poor predictor of C residence time in soil, at least over short time periods. We ascribe this lack of observed difference to the high degree of microbial functional redundancy in soil, the strong influence of environmental factors and the uncertainties inherent in the use of short term biological assays to represent pedogenic processes which have taken ca. 10,000 y to become manifest.     

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

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

ECe prediction from EC1:5 in inland salt-affected soils collected from Khorat and Sakhon Nakhon basins,Thailand

ABSTRACT

We estimate the electrical conductivity of saturated soil paste extract (ECe) from electrical conductivity of a 1:5 soil-water dilution ratio (EC_1:5) in Northeastern Thailand. Soil samples of various textures and salinity collected from Sakhon Nakhon basin were used to develop multiple regression models, from which the linear model was chosen and was validated on soil samples from the Khorat basin. Comparison with previous models indicated that most linear models gave a good fit, but the non-linear models either over or underestimated the measured values. The models performed very well for low values of EC_e (<5 dS m^?1), while the prediction errors increased significantly for EC_e levels >35 dS m^?1. The present model performed well at various EC_e levels and can be used to predict salinity levels for soils weathered from salt deposits in sedimentary rocks with similar rock formation in countries like Malaysia, Vietnam, Cambodia, and Laos.     

Zinc toxicity on N2O reduction declines with time in laboratory spiked soils and is undetectable in field contaminated soils

Denitrification assays in soils spiked with zinc salt have shown inhibition of the N₂O reduction resulting in increased soil N₂O fluxes with increasing soil Zn concentration. It is unclear if the same is true for environmentally contaminated soils. Net production of N₂O and N₂ was monitored during anaerobic incubations (25 °C, He atmosphere) of soils freshly spiked with ZnCl₂ and of corresponding soils that were gradually enriched with metals (mainly Zn) in the field by previous sludge amendments or by corrosion of galvanized structures. Total denitrification activity (i.e. the sum of N₂O+N₂ production rate) was not inhibited by freshly added Zn salts up to 1600 mg Zn kg⁻¹, whereas N₂O reduction decreased by 50% (EC₅₀) at total Zn concentrations of 231 mg Zn kg⁻¹ (ZEV soil) and 368 mg Zn kg⁻¹ (TM soil). In contrast, N₂O reduction was not reduced by soil Zn in any of the field contaminated soils, even at total soil Zn or soil solution Zn concentrations exceeding more than 5 times corresponding EC₅₀'s of the freshly spiked soil. The absence of adverse effects in the field contaminated soils was unrelated to soil NO₃ or organic matter concentration. Ageing (2-8 weeks) and soil leaching after spiking reduced the toxicity of Zn on N₂O reduction, either expressed as total Zn or soil solution Zn, suggesting adaptation reactions. However, no full recovery after spiking was identified at the largest incubation period in one soil. In addition, the denitrification assay performed with sewage sludge showed elevated N₂O release in Zn contaminated sludges (>6000 mg Zn kg⁻¹ dry matter) whereas this was not observed in low Zn sludge (<1000 mg Zn kg⁻¹ dry matter) suggesting limits to adaptation reactions in the sludge particles. It is concluded that the use of soils spiked with Zn salts overestimates effects on N₂O reduction. Field data on N₂O fluxes in sludge amended soils are required to identify if metals indeed promote N₂O emissions in sludge amended soils.     

Impact of Cow Dung Manure on the Solubility of Copper,Lead, and Zinc in Urban Garden Soils from Northern Nigeria

Maintaining the quality of groundwater is a major consideration when developing management practices to effectively use cow dung manure (CDM) as a nutrient source and soil conditioner in agricultural production systems. This study examines the effect of CDM on the solubility of copper (Cu), lead (Pb), and zinc (Zn) in urban garden fields from Kaduna under long-term vegetable production. Soil samples were collected from Kakau, Kakuri, Trikaniya, and Romi in Kaduna metropolis in northern Nigeria. Soil–manure mixtures at the rate of 100 g CDM kg^?1 soil were incubated for 2 weeks and analyzed for exchangeable [0.1 M calcium chloride (CaCl₂)–extractable], mobile [1 M ammonium nitrate (NH₄NO₃)–extractable], and potentially labile [0.05 M ethylenediaminetetraacetic acid (EDTA)–extractable] copper (Cu), lead (Pb), and zinc (Zn). Addition of CDM increased exchangeable Cu in Kakuri and Romi and exchangeable Pb in Kakau and Kakuri, but decreased exchangeable Zn across the sites. The addition of CDM increased mobile Cu and Pb in all the sites. Although there was a decrease in mobile Zn in Kakau and Romi after the soil–manure incubation period, mobile Zn increased in Trikaniya and Kakuri. Furthermore, CDM decreased potentially labile Cu, Pb, and Zn in all the sites except for Romi, which increased labile Cu. To sustain the quality of soil and minimize groundwater pollution and food chain contamination, use of CDM in urban garden soils polluted with Cu, Pb, and Zn should be regulated or discouraged entirely to reduce the mobility of these metals.     

Legacy phosphorus in calcareous soil under 33 years of P fertilizer application: Implications for efficient P management in agriculture

Phosphorus (P) fertilizers have long been applied in agriculture. However, the influence of long-term P addition on the evolution of soil P fertility and legacy P characteristics have not been well-documented. Herein, literature data were collected from the Chinese National Knowledge Infrastructure Database (CNKI) to explore the evolution of soil P fertility after 33 years of application of P fertilizer; different soil samples were collected from cropland and adjacent uncultivated land to analyse the distribution of P fractions at different soil depths (0–0.8 m) using Guppy's sequential P extraction method. We found that soil Olsen-P significantly increased by 3.6-fold (from 7.2 mg kg⁻¹ in 1981 to 25.9 mg kg⁻¹ in 2013) after 33 years of P application, while total P increased slightly. The ratios of inorganic P fractions in cropland to those uncultivated land followed NaHCO₃-P (1.47) > NaOH-P (1.38) > resin-P (1.37) > residue-P (1.17) > HCl-P (1.11), suggesting that long-term P addition contributed more to labile and moderately labile P rather than non-labile P. Moreover, a principal component analysis could distinguish between cropland and uncultivated land, indicating that long-term application of P fertilizer changed soil P characteristics. Compared to uncultivated land, soil NaHCO₃-P in cropland was closely associated with soil organic C, total nitrogen and carbonate. Collectively, our findings highlight that soil legacy P was notably increased after long-term of P application, and a large portion of the applied P remained in labile and moderately labile forms. Therefore, soil legacy P can be recommended as a useful P management tool.     

Appraisal of Some Soil Tests for Zinc Availability to Late‐Sown Wheat Grown in Mollisols

Abstract

Five soil extractants, namely, 0.005 M diethylene triamine pentaacetic acid (DTPA) (pH 7.3), 0.005 M DTPA+1 M ammonium bicarbonate (pH 7.6), Mehlich 3, 0.01 M ethylene diamine tetraacetic acid (EDTA)+0.05 M ammonium carbonate (pH 8.6), and 1 M magnesium chloride (MgCl₂) (pH 6.0), were evaluated to predict the response of wheat to zinc (Zn) application in Mollisols. These extractants could be arranged in the following decreasing order of their Zn extracting power: Mehlich 3>0.005 M DTPA+1 M ammonium bicarbonate>0.01 M EDTA+0.05 M ammonium carbonate>0.005 M DTPA>1 M MgCl₂. The critical limits of Zn in soil, below which the yield response to late sown wheat (var. UP‐2338) to Zn application could be expected, were 0.57 mg 0.005 M DTPA (pH 7.3) extractable and 1.72 mg Mehlich 3–extractable Zn kg^?1 soil. The critical limit of Zn in whole shoot at 60 days after emergence was found to be 26.1 mg Zn kg^?1 plant tissue. The DTPA and Mehlich 3–extractable soil Zn also correlated significantly and positively with Zn concentration in whole shoot at 60 days after emergence and total Zn uptake by wheat at harvest.     

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

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

Changes of arbuscular mycorrhizal traits and community structure with respect to soil salinity in a coastal reclamation land

A comprehensive knowledge on the relationship between soil salinity and arbuscular mycorrhizal fungi (AMF) is vital for a deeper understanding of ecosystem functioning under salt stress conditions. The objective of this study was to determine the effects of soil salinity on AMF root colonization, spore count, glomalin related soil protein (GRSP) and community structure in Saemangeum reclaimed land, South Korea. Soil samples were collected and grouped into five distinct salt classes based on the electrical conductivity of soil saturation extracts (EC_se). Mycorrhizal root colonization, spore count and GRSP were measured under different salinity levels. AMF community structure was studied through three complementary methods; spore morphology, terminal restriction fragment length polymorphism (T-RFLP) and denaturing gradient gel electrophoresis (DGGE). Results revealed that root colonization (P < 0.01), spore count (P < 0.01) and GRSP (P < 0.01) were affected negatively by soil salinity. Spore morphology and T-RFLP data showed predominance of AMF genus Glomus in Saemangeum reclaimed land. T-RFLP and DGGE analysis revealed significant changes in diversity indices between non (EC_se < 2 dS/m) and extremely (EC_se > 16 dS/m) saline soil and confirmed dominance of Glomus caledonium only in soils with EC_se < 8 dS/m. However, ribotypes of Glomus mosseae and Glomus proliferum were ubiquitous in all salt classes. Combining spore morphology, T-RFLP and DGGE analysis, we could show a pronounced effect in AMF community across salt classes. The result of this study improve our understanding on AMF activity and dominant species present in different salt classes and will substantially expand our knowledge on AMF diversity in reclaimed lands.     

Surface runoff phosphorus (P) loss in relation to phosphatase activity and soil P fractions in Florida sandy soils under citrus production

Phosphorus losses by surface runoff from agricultural lands have been of public concern due to increasing P contamination to surface waters. Five representative commercial citrus groves (C1-C5) located in South Florida were studied to evaluate the relationships between P fractions in soils, surface runoff P, and soil phosphatase activity. A modified Hedley P sequential fractionation procedure was employed to fractionate soil P. Soil P consisted of mainly organically- and Ca/Mg-bound P fractions. The organically-bound P (biological P, sum of organic P in the water, NaHCO₃ and NaOH extracts) was dominant in the acidic sandy soils from the C2 and C3 sites (18% and 24% of total soil P), whereas the Ca/Mg-bound P (HCl-extractable P) accounted for 45-60% of soil total P in the neutral and alkaline soils (C1, C4 and C5 soils). Plant-available P (sum of water and NaHCO₃ extractable P fractions) ranged from 27 to 61 mg P kg⁻¹ and decreased in the order of C3>C4>C1>C2>C5. The mean total P concentrations (TP) in surface runoff water samples ranged from 0.51 to 2.64 mg L⁻¹. Total P, total dissolved P (TDP), and PO₄³⁻-P in surface runoff were significantly correlated with soil biological P and plant-available P forms (p<0.01), suggesting that surface runoff P was directly derived from soil available P pools, including H₂O- and NaHCO₃- extractable inorganic P, water-soluble organic P, and NaHCO₃- and NaOH-extractable organic P fractions, which are readily mineralized by soil microorganisms and/or enzyme mediated processes. Soil neutral (55-190 mg phenol kg⁻¹ 3 h⁻¹) and natural (measured at soil pH) phosphatase activities (77-295 mg phenol kg⁻¹ 3 h⁻¹) were related to TP, TDP, and PO₄³⁻-P in surface runoff, and plant-available P and biological P forms in soils. These results indicate that there is a potential relationship between soil P availability and phosphatase activities, relating to P loss by surface runoff. Therefore, the neutral and natural phosphatase activities, especially the natural phosphatase activity, may serve as an index of surface runoff P loss potential and soil P availability.