Temperature, water content and wet-dry cycle effects on DOC production and carbon mineralization in agricultural peat soils

Agricultural peat soils in the Sacramento-San Joaquin Delta, California have been identified as an important source of dissolved organic carbon (DOC) and trihalomethane precursors in waters exported for drinking. The objectives of this study were to examine the primary sources of DOC from soil profiles (surface vs. subsurface), factors (temperature, soil water content and wet-dry cycles) controlling DOC production, and the relationship between C mineralization and DOC concentration in cultivated peat soils. Surface and subsurface peat soils were incubated for 60 d under a range of temperature (10, 20, and 30 °C) and soil water contents (0.3-10.0 g-water g-soil⁻¹). Both CO₂-C and DOC were monitored during the incubation period. Results showed that significant amount of DOC was produced only in the surface soil under constantly flooded conditions or flooding/non-flooding cycles. The DOC production was independent of temperature and soil water content under non-flooded condition, although CO₂ evolution was highly correlated with these parameters. Aromatic carbon and hydrophobic acid contents in surface DOC were increased with wetter incubation treatments. In addition, positive linear correlations (r²=0.87) between CO₂-C mineralization rate and DOC concentration were observed in the surface soil, but negative linear correlations (r²=0.70) were observed in the subsurface soil. Results imply that mineralization of soil organic carbon by microbes prevailed in the subsurface soil. A conceptual model using a kinetic approach is proposed to describe the relationships between CO₂-C mineralization rate and DOC concentration in these soils.     

Cu and Ni Mobility and Bioavailability in Sequentially Conditioned Soils

The potential ecological hazard of metals in soils may be measured directly using a combination of chemical and biological techniques or estimated using appropriate ecological models. Terrestrial ecotoxicity testing has gained scientific credibility and growing regulatory interest; however, toxicity of metals has often been tested in freshly amended soils. Such an approach may lead to derivation of erroneous toxicity values (EC₅₀) and thresholds. In this study, the impact of metal amendments on soil ecotoxicity testing within a context of ion competition was investigated. Four coarse-textured soils were amended with copper (Cu) and nickel (Ni), incubated for 16 weeks and conditioned by a series of total pore water replacements. Rhizon^TM extracted pore water Cu, Ni, pH and dissolved organic carbon (DOC) concentrations were measured after each replacement. Changes in ecotoxicity of soil solutions were also monitored using a lux-based biosensor (Escherichia coli HB101 pUCD607) and linked to variations in soil solution metal and DOC concentrations, pH and selected characteristics of the experimental soils (exchangeable calcium (Ca) and magnesium (Mg)). Prior to conditioning of soils, strong proton competition produced relatively high EC₅₀ values (low toxicity) for both, Cu and Ni. The successive replacement of pore waters lead to a decline of labile pools of metals, DOC and alleviated the ecotoxicological protective effect of amendment impacted soil solution chemistry. Consequently, derived ecotoxicity values and toxicity thresholds were more reflective of genuine environmental conditions and the relationships observed more consistent with trends reported in historically contaminated soils.     

Dissolved Organic Carbon in Association with Water Soluble Nutrients and Metals in Soils from Lake Okeechobee Watershed, South Florida

Water quality of Lake Okeechobee has been a major environmental concern for many years. Transport of dissolved organic matter (DOM) in runoff water from watershed is critical to the increased inputs of nutrients (N and P) and metals (Cu and Zn). In this study, 124 soil samples were collected with varying soil types, land uses, and soil depths in Lake Okeechobee watershed and analyzed for water-extractable C, N, P, and metals to examine the relationship between dissolved organic carbon (DOC) and water soluble nutrients (N and P) and metals in the soils. DOC in the soils was in 27.64?C400 mg kg^?1 (69.30 mg kg^?1 in average) and varied with soil types, land uses, and soil depth. The highest water-extractable DOC was found in soils collected in sugar cane and field crops (277 and 244 mg kg^?1 in average, respectively). Water soluble concentrations of N and P were in the range of 6.46?C129 and 0.02?C60.79 mg kg^?1, respectively. The ratios of water-extractable C/N and C/P in soils were in 0.68?C12.52 (3.23 in average) and 3.19?C2,329 (216 in average), and varied with land uses. The lowest water-extractable C/N was observed in the soils from dairy (1.66), resident (1.79), and coniferous forest (4.49), whereas the lowest water-extractable C/P was with the land uses of dairy (13.1) and citrus (33.7). Therefore, N and P in the soils under these land uses may have high availability and leaching potential. The concentrations of water soluble Co, Cr, Cu, Ni, and Zn were in the ranges of?<?method detection limit (MDL)?C0.33, <MDL?C0.53, 0.04?C2.42, <MDL?C0.71, and 0.09?C1.13 mg kg^?1, with corresponding mean values of 0.02, 0.01, 0.50, 0.07, and 0.37 mg kg^?1, respectively. The highest water soluble Co (0.10 mg kg^?1), Cr (0.26 mg kg^?1), Ni (0.31 mg kg^?1), and Zn (0.80 mg kg^?1) were observed in soils under the land use of sugar cane, whereas the highest Cu (1.50 mg kg^?1) was with field crop. The concentration of DOC was positively correlated with total organic carbon (TOC) (P <0.01), water soluble N (P <0.01), electrical conductivity (EC, P <0.01), and water soluble Co, Cr, Ni, and Zn (P <0.01), and Cu (P <0.05), whereas water soluble N was positively correlated with water soluble P, Cu, and Zn (P <0.01) in soils. These results indicate that the transport of DOC from land to water bodies may correlate with the loss of macro-nutrients (N, P), micro-nutrients (Cu, Zn, and Ni), and contaminants (Cr and Co) as well.     

Speciation of cadmium,copper, lead,and zinc in contaminated soils

Abstract

To investigate the activity of free cadmium (Cd²⁺), copper (Cu²⁺), lead (Pb²⁺), and zinc (Zn²⁺) ions and analyze their dependence on pH and other soil properties, ten contaminated soils were sampled and analyzed for total contents of Cd, Cu, Pb, and Zn (Cd_T, Cu_T, Pb_T, and Zn_T, respectively), 0.43 MHNO₃‐extractable Cd, Cu, Pb, and Zn (Cd_N, Cu_N, Pb_N, and Zn_N, respectively), pH, dissolved organic matter (DOC), cation exchange capacity (CEC), ammonium oxalate extractable aluminum (Al) and iron (Fe), and dissolved calcium [Ca²⁺]. The activity of free Pb²⁺, Cd²⁺, Cu²⁺, and Zn²⁺ ions in soil solutions was determined using Donnan equilibrium/graphite furnace atomic absorption (DE/GFAA). The solubility of Cd in soils varied from 0.16 to 0.94 μg L^‐1, Cu from 3.43 to 7.42 μg L^‐1, Pb from 1.23 to 5.8 μg L^‐1, and Zn from 24.5 to 34.3 μg L^‐. In saturation soil extracts, the activity of free Cd²⁺ ions constituted 42 to 82% of the dissolved fraction, for Cu²⁺the range was 0.1 to 7.8%, for Pb²⁺ 0.1 to 5.1% and for Zn²⁺2 to 72%. The principal species of Cd, Cu, Pb, and Zn in the soil solution is free metal ions and hydrolyzed ions. Soil pH displayed a pronounced effect on the activity of free Cd²⁺, Cu^2t, Pb²⁺, and Zn²⁺ ions.     

Copper distribution and acid-base mobilization in vineyard soils and sediments from Galicia (NW Spain)

In northern Spain and elsewhere in the world, many vineyards are located on steep slopes and are susceptible to accelerated soil erosion. Contaminants, notably Cu, originating from repeated application of copper‐based fungicides to the vines to prevent mildew, are transported and stored in the sediments deposited close to valley bottoms. In this study, the contents and distribution of Cu in 17 soil samples and 21 sediment samples collected from vineyard stands were determined. In addition, the effect of pH on Cu release from vineyard soils and sediments was quantified. The total Cu content (Cu_T) in the soils varied between 96 and 583 mg kg^?1, and was between 1.2 and 5.6 times greater in sediment samples. The mean concentration of potentially bioavailable Cu (Cu_EDTA) in the sediments was 199 mg kg^?1 (46% of Cu_T), and was 80 mg kg^?1 (36% of Cu_T) in the soils. Copper bound to soil organic matter (Cu_OM) was the dominant fraction in the soils (on average, 53% of the Cu_T), while in sediment samples Cu_OM values varied between 37 and 712 mg kg^?1 and were significantly greater (P < 0.01) than in the soils. Copper associated with non‐crystalline inorganic components (Cu_IA) was the second most important fraction in the sediments, in which it was 3.4 times greater than in the soils. Release of Cu due to changes in the pH followed a U‐shaped pattern in soils and sediments. The release of Cu increased when the pH decreased below 5.5 due to the increased solubility of the metal at this pH. When the pH increased above 7.5, Cu and organic matter were released simultaneously.     

The UV‐absorbance of dissolved organic matter predicts the fivefold variation in its affinity for mobilizing Cu in an agricultural soil horizon

It is well established that dissolved organic matter (DOM) mobilizes copper (Cu) in soils but it is unknown to what extent variable DOM quality affects this. During a 5 month period, 250 leachates of an uncontaminated agricultural soil were sampled at 45 cm depth using passive capillary wick samplers. The dissolved Cu and organic carbon (DOC) concentrations varied sevenfold and were weakly correlated (r = 0.56). The [Cu] : [DOC] ratio varied fivefold and exhibited a significant positive correlation (r = 0.77) with the specific UV‐absorbance of DOM at 254 nm (SUVA), indicating that the more aromatic DOM had higher Cu affinity. The dissolved Cu concentrations were predicted by an assemblage model in WHAM6 using the composition of the solid phase above the wick samplers and that of the solution, including DOC. The predicted [Cu] : [DOC] ratio was almost constant when assuming default DOM properties with 65% of all DOM active as fulvic acid (%AFA). The %AFA was subsequently varied proportionally to the SUVA of DOM and using the SUVA of pure FA (SUVA_FA) as a fitting parameter. In that case, the variation in the predicted [Cu] : [DOC] ratio was much larger and the predicted Cu concentrations were within a factor of 1.4 of the measured values for 90% of the samples. The fitted SUVA_FA was 38 l g^?1 cm^?1, in excellent agreement with that of Suwannee River FA (SUVA_FA = 37 l g^?1 cm^?1). It is concluded that the DOM quality, e.g. the aromaticity, should be taken into account when estimating Cu mobility in soils.     

General purpose Freundlich isotherms for cadmium,copper and zinc in soils

Assessing the accumulation and transport of trace metals in soils and the associated toxicological risks on a national scale requires generally applicable sorption equations. Therefore Freundlich equations were derived for Cd, Zn and Cu using multiple linear regression on batch sorption data from the literature with a wide variety of soil and experimental characteristics, and metal concentrations ranging over five orders of magnitude. Equations were derived based on both total dissolved metal concentrations and free metal activities in solution. Free metal activities were calculated from total metal concentrations taking into account ionic activity, and inorganic (all metals) and organic complexation (Cu only). Cadmium and Zn were present in solution predominantly as free ions, while Cu was present as organic complexes. Since actual dissolved organic carbon (DOC) concentrations were not available they were estimated using an empirical field relation between DOC and organic matter content. The logarithmic transformation of the Freundlich constant for Cd was regressed on the logarithmic transformations of cation exchange capacity (CEC) (H⁺) and dissolved Ca, and for Zn with CEC and (H⁺). For Cu the log–log regression model of the Freundlich constant included the solid:solution ratio of the batch to account for dilution of DOC in the batch as compared with the field. The explained variance for the fitted Freundlich equations was 79% for Cd, 65% for Cu and 83% for Zn, using log-transformed adsorbed concentrations and soil solution activities. The Freundlich adsorption models underestimated metal contents determined from 1 m HNO₃ digestion on field samples, up to a factor of 6 (Cd and Cu) or 10 (Zn).     

铜对土壤中功夫菊酯和氯氰菊酯迁移和扩散的影响

Repeated applications of bordeaux mixture （a blend of copper sulfate and calcium hydroxide） and pyrethroid insecticides （Pys） have led to elevated copper （Cu） and Pys concentrations in vineyard surface soils. To understand the potential influence of Cu on the fate of Pys in the soil environment, we selected two Pys, cypermethrin （CPM） and lambda-cyhalothrin （λ-CHT）, and two typical Chinese vineyard soils, Haplic Acrisol and Luvic Phaeozem, as experimental samples. The dissipation experiment was conducted at room temperature in the dark, and the transport of both Pys through the soils was investigated using soil thin-layer chromatography. The results showed that the transport of Pys in both soils increased as the Cu²⁺ concentration increased from 0 to 100 mg L^-1 , and Pys were more transportable in Haplic Acrisol （HA） than in Luvic Phaeozem （LP） under the same experimental conditions. For CPM, only 100 mg L^-1 of Cu²⁺ significantly （P<0.05） increased Pys transport through both soils relative to water. Lambda-CHT was significantly （P<0.05） transported through HA by all the Cu²⁺ concentrations compared to water, and all but the 1 mg L^-1 of Cu²⁺ significantly （P<0.05） increased the transport of λ-CHT through LP relative to water. However, the dissipation rates of CPM and λ-CHT decreased with the addition of Cu to soils. Our findings suggest that the risk of groundwater contamination by Pys increases in the soils with elevated Cu concentrations.     

Moisture pulses,trace gas emissions and soil C and N in cheatgrass and native grass-dominated sagebrush-steppe in Wyoming,USA

Effects of large-scale weed invasion on the nature and magnitude of moisture-pulse-driven soil processes in semiarid ecosystems are not clearly understood. The objective of this study was to monitor carbon dioxide (CO₂) and nitrous oxide (N₂O) emissions and changes in soil carbon (C) and nitrogen (N) following the application of a water pulse in Wyoming big sagebrush (Artemisia tridentata ssp. wyomingensis) communities dominated by the exotic annual grass cheatgrass (Bromus tectorum) and by the native perennial grass western wheatgrass (Pascopyrum smithii). Sampling locations were established in shrub interspaces dominated by B. tectorum and P. smithi and beneath shrub canopies adjacent to interspaces dominated by B. tectorum and P. smithi, where no grass was present. Soils were classified as fine-loamy, mixed, Borollic Haplargids. Soil samples (0–10 cm) and air samples were collected at 0, 4, 8, 24, 49, 72, and 216 h following additions of 25.4 mm of water. Soil samples were analyzed for dissolved organic carbon (DOC), microbial biomass carbon (MBC), extractable ammonia (NH₄⁺), extractable nitrate (NO₃^?), and dissolved organic nitrogen (DON). Grass species induced differences in soil nitrification, N₂O and CO₂ emissions, and the quantity and timing of labile C available to microbial populations responding to increased moisture availability. In the first 8-h phase after wetting P. smithii soils had the greatest CO₂ emissions compared to other soils but B. tectorum soils had the greatest N₂O emissions and the greatest increases in CO₂ emissions relative to before wetting. Microbial biomass C in B. tectorum interspace soils increased rapidly but the response was short-lived despite sufficient water availability. After the first 8 h of soil response to wetting, the observed MBC declines in B. tectorum interspace coincided with disproportional DOC and DON concentration increases. Similar DOC and DON increases were also observed in B. tectorum soils beneath shrub canopy. In contrast, DOC and DON concentrations in P. smithii soils remained unaffected by soil wetting and small MBC increases observed during the first 8-h phase did not decline as rapidly as in B. tectorum interspace soils. In conclusion, summer drying-wetting cycles that occur frequently in areas invaded by B. tectorum can accelerate rates of nitrification and C mineralization, and contribute significantly to trace gas emissions from sagebrush-steppe grasslands. With frequent summer rainfall events, the negative consequences B. tectorum presence in the ecosystem can be significant.     

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.     

Copper Accumulation in a Reservoir Ecosystem Following Copper Sulfate Treatment (St. Germain Les Belles, France)

Copper sulfate (CuSO₄) addition to freshwater for phytoplankton control has been practiced for decades, and remains the most effective algicidal treatment for numerous managed water bodies. A reservoir in the centre of France was the site for an investigation of copper distribution in aquatic systems after a copper sulfate treatment. Results of monitoring showed a rapid conversion of dissolved Cu to particulate forms, with significant accumulation in the sediments. Total sediment Cu content increased from approximately 37.7 to 45.4 μg g^-1 dry weight after the first treatment. Sequential extraction suggested that a significant portion of the sediment-borne Cu was associated with the organic fraction which may release Cu to the water column, although significant release would occur only under extreme changes in water chemistry. Based upon measured Cu concentrations, flows at the down-stream water, and known mass applied during treatment, mass balance calculations indicated that approximately 17% of the Cu was exported from the reservoir over a 70 day period following a 196 μg L^-1 Cu²⁺ (as CuSO₄·5H₂O) treatment.Copper bioaccumulation by a moss, Fontinalis antipyretica in the down-stream water showed that it was possible to distinguish between a treated and an untreated area. The impact of copper treatmentin the down-stream reservoir could be followed using mosses. There is a distance effect which could be exploited to determine potential copper impact for example. The largest amount of copper was probably adsorbed on downstream sediment or lost in running water. Thirty days after copper sulfate addition, Fontinalis still indicatedcopper exposure.     

Response of soil constituents to freeze-thaw cycles in wetland soil solution

Soil freeze-thaw cycles in the winter-cold zone can substantially affect soil carbon, nitrogen and phosphorus cycling, and deserve special consideration in wetlands of cold climates. Semi-disturbed soil columns from three natural wetlands (Carex marsh, Carex marshy meadow and Calamagrostis wet grassland) and a soybean field that has been reclaimed from a wetland were exposed to seven freeze-thaw cycles. The freeze-thaw treatments were performed by incubating the soil columns at −10 °C for 1 d and at 5 °C for 7 d. The control columns were incubated at 5 °C for 8 d. After each freeze-thaw cycle, the soil solution was extracted by a solution extractor installed in each soil layer of the soil column, and was analyzed for dissolved organic carbon (DOC), NH₄⁺-N, NO₃⁻-N and total dissolved phosphorus (TDP). The results showed that freeze-thaw cycles could increase DOC, NH₄⁺-N and NO₃⁻-N concentrations in soil solutions, and decrease TDP concentrations. Moreover, the changes of DOC, NH₄⁺-N, NO₃⁻-N and TDP concentrations in soil solutions caused by freeze-thaw cycles were different in various sampling sites and soil layers. The increments of DOC concentrations caused by freeze-thaw cycles were greater in the wetland soil columns than in the soybean field soil columns. The increments of NH₄⁺-N concentrations caused by freeze-thaw cycles decreased with the increase of soil depth. The depth variation in the increments of NO₃⁻-N concentrations caused by freeze-thaw cycles in the wetland soil columns was different from that in the soybean field soil columns. The decrements of TDP concentrations caused by freeze-thaw cycles were greater in columns of Carex marsh and Carex marshy meadow than in columns of Calamagrostis wet grassland and the soybean field. The study results provide information on the timing of nutrient release related to freezing and thawing in natural versus agronomic soils, and have implications for the timing of nutrient application in farm fields in relation to water quality protection.     

Contributions of ant mounds to soil carbon and nitrogen pools in a marsh wetland of Northeastern China

Ant mounds often occur at high densities in marsh wetlands. However, little information is available regarding their impacts on soil nutrient pools in these ecosystems. We studied C_org, dissolved organic carbon (DOC), total nitrogen (TN), NO₃⁻ and NH₄⁺ concentrations in above-ground ant mounds and in soils under mounds for three ant species (Lasius flavus, Lasius niger and Formica candida), and estimated their contribution to the total soil nutrient pools in a marsh wetland. Ant impacts were greatest in above-ground soils. All measured nutrient concentrations in above-ground mounds were significantly higher than the average values in reference soils (upper 25 cm). However, except for DOC, no significant differences for nutrient concentrations existed between soils under mounds and reference soils. The impacts of ant mounds on soil C and nutrient concentrations varied by ant species. L. niger above-ground mounds stored less C_org, TN and NO₃⁻ than F. candida and L. flavus mounds, or reference soils. At the ecosystem scale, soils in above-ground mounds and under ant mounds all contained less C_org per hectare than the reference soils. Total amounts in nutrient pools from mounds of the three ant species comprised from 5.3% to 7.6% of the total in natural marsh soils. More importantly, ant mounds increased the spatial heterogeneity of nutrient pools. Thus, ant mounds can be important to a fully integrated understanding of the structure and function of wetland nutrient cycles and balances.     

Responses of soil dissolved organic matter to long-term plantations of three coniferous tree species

Tree species have significant effects on the availability and dynamics of soil organic matter. In the present study, the pool sizes of soil dissolved organic matter (DOM), potential mineralizable N (PMN) and bio-available carbon (C) (measured as cumulative CO₂ evolution over 63 days) were compared in soils under three coniferous species — 73 year old slash (Pinus elliottii), hoop (Araucaria cunninghamii) and kauri (Agathis robusta) pines. Results have shown that dissolved organic N (DON) in hot water extracts was 1.5–1.7 times lower in soils under slash pine than under hoop and kauri pines, while soil dissolved organic C (DOC) in hot water extracts tended to be higher under slash pine than hoop and kauri pines but this was not statistically significant. This has led to the higher DOC:DON ratio in soils under slash pine (32) than under hoop and kauri pines (17). Soil DOC and DON in 2 M KCl extracts were not significantly different among the three tree species. The DOC:DON ratio (hot water extracts) was positively and significantly correlated with soil C:N (R² = 0.886, P < 0.01) and surface litter C:N ratios (R² = 0.768, P < 0.01), indicating that DOM was mainly derived from litter materials and soil organic matter through dissolution and decomposition. Soil pH was lower under slash pine (4.5) than under hoop (6.0) and kauri (6.2) pines, and negatively correlated with soil total C, C:N ratio, DOC and DOC:DON ratio (hot water extracts), indicating the soil acidity under slash pine favored the accumulation of soil C. Moreover, the amounts of dissolved inorganic N, PMN and bio-available C were also significantly lower in soils under slash pine than under hoop and kauri pines. It is concluded that changes in the quantity and quality of surface litters and soil pH induced by different tree species largely determined the size and quality of soil DOM, and plantations of hoop and kauri pine trees may be better in maintaining long-term soil N fertility than slash pine plantations.     

Toxicity of Sb and Cu in Sewage Sludge to Terrestrial Plants (Lettuce,Oat, Radish), and of Sludge Elutriate to Aquatic Organisms (Daphnia and Lemna) and its Interaction

Antimony (Sb) and Copper (Cu) are two metals of major concern in sewage sludge. Antimony because its use in society is increasing and this might lead to increased Sb concentrations in sludge. Copper because its total volume in use in society is large and because of corrosion from water pipes it is most difficult to reduce the Cu concentrations in sludge. Fresh digested sewage sludge was spiked with Cu or Sb and the sludge was cultivated with oat (Avena sativa), lettuce (Lactuca sativa) or radish (Raphanus sativus). Elutriates from the cultivated sludge were tested for toxicity with Lemna minor (7-d growth) and Daphnia magna (48 h immobility). Before cultivation the elutriates were toxic to Lemna and Daphnia due to high concentrations of ammonia (NH₃) and nitrite (NO₂ ^-). Cultivation decreased the concentrations of both NH₃ and NO₂ ^-, thereby reducing the impact of these compounds in the toxicity tests. Cultivation also decreased the metal concentrations and pH. Daphnia magna was the most sensitive test organism in this study with a 48 h EC₅₀ of 1130 mg Cu kg^-1 dry wt and 5 mg Sb kg^-1 dry wt in elutriates from sludge cultivated with oat. In sludge cultivated with radish the 48 h EC₅₀ was 1700 mg Cu kg^-1 dry wt and 22 mg Sb kg^-1 dry wt. The effect of Cu could be predicted by pH and Cu concentrationin the elutriate, but the effect of Sb could not solely be explained by its concentration in the elutriate.     

Variability and relationships between Pb,Cu, and Zn concentrations in soil solutions and forest floor leachates at heavily polluted sites

Seasonal variability of Cu, Pb, and Zn concentrations in litter leachates and soil solutions was examined in an afforested zone surrounding a copper smelter in SW Poland. Litter leachates (with zero‐tension lysimeters) and soil solutions (with MacroRhizon suction‐cup samplers, installed at a depth of 25–30 cm) were collected monthly at three sites differing in contamination levels in the years 2009 and 2010 (total Cu: 2380, 439, and 200 mg kg^–1, respectively). Concentrations of Cu in the litter leachate were correlated with dissolved organic C (DOC), whereas Zn and Pb were mainly related to leachate pH. Metal concentrations in the soil solution were weakly influenced by their total content in soils and the monthly fluctuations reached 300, 600, and 700% for Cu, Pb, and Zn, respectively. Metal concentrations in soil solutions (Cu 110–460 μg L^–1; Zn 20–1190 μg L^–1; Pb 0.5–36 μg L^–1) were correlated with their contents in the litter leachates. Chemical speciation, using Visual Minteq 3.0, proved organically‐complexed forms even though the correlations between metal concentrations and soil solution pH and DOC were statistically insignificant. The flux of organically‐complexed metals from contaminated forest floors is believed to be a direct and crucial factor affecting the actual heavy metal concentrations and their forms in the soil solutions of the upper mineral soil horizons.     

Effects of Changed Soil Conditions on the Mobility of Trace Metals in Moderately Contaminated Urban Soils

Changes in the soil chemical environment can be expected to increase the leaching of trace metals bound in soils. In this study the mobility of trace metals was monitored in a column experiment for two contaminated urban soils. Four different treatments were used (i.e. rain, acid rain, salt and bark). Leachates were analysed for pH, dissolved organic carbon (DOC) and for seven trace metals (cadmium (Cd), chromium (Cr), copper (Cu), mercury (Hg), nickel (Ni), lead (Pb) and zinc (Zn)). The salt treatment produced the lowest pH values (between 5 and 6) in the effluent whereas the DOC concentration was largest in the bark treatment (40–140 mg L^?1) and smallest in the salt and acid treatments (7–40 mg L^?1). Cadmium, Ni and Zn were mainly mobilised in the salt treatment, whereas the bark treatments produced the highest concentrations of Cu and Pb. The concentrations of Cu, Cr, and Hg were strongly correlated with DOC (r ²?=?0.90, 0.91 and 0.96, respectively). A multi-surface geochemical model (SHM-DLM) produced values for metal dissolution that were usually of the correct magnitude. For Pb, however, the model was not successful indicating that the retention of this metal was stronger than assumed in the model. For all metals, the SHM-DLM model predicted that soil organic matter was the most important sorbent, although for Pb and Cr(III) ferrihydrite was also important and accounted for between 15 and 50% of the binding. The results confirm the central role of DOC for the mobilization of Cu, Cr, Hg and Pb in contaminated soils.     

Copper Accumulations in Soils,Coffee, Banana,and Bean Plants Following Copper-Based Fungicides in Coffee Farms in Arusha and Kilimanjaro Regions,Tanzania

This study was carried out to investigate the levels of copper (Cu) contamination in coffee fields in Kilimanjaro and Arusha regions, Tanzania, to increase the database on the contamination of soils by Cu-based fungicides in coffee fields. Surface (0–20 cm deep) soil samples were collected from different farms in Kilimanjaro and Arusha regions. Coffee, banana, and bean plant samples were collected from the locations of soil sampling. Soil and plant samples were analyzed at the Department of Soil Science, Sokoine University of Agriculture, Morogoro, Tanzania. It was found that the calcium chloride (CaCl₂)–extractable Cu was less than the detection limit of flame atomic absorption spectrometry. Diethylenetriaminepentaacetic acid (DTPA)–extractable (24 to 366 mg Cu kg^?1 soil) and aqua regia–extractable (80 to 806 mg Cu kg^?1 soil) Cu levels were high enough to raise environmental alarm (based on European Union guidelines) in the Cu fungicide–treated soils as compared with natural Cu levels in untreated soils (1 to 12 mg Cu kg^?1 soil for DTPA and 22 to 32 mg Cu kg^?1 soil for aqua regia–extractable Cu). Coffee, banana, and bean plants grown on soils contaminated by Cu fungicides had varied concentrations of Cu that were greater than the concentrations of Cu in the plants collected from the uncontaminated soils. Stepwise regression analysis carried out to investigate the relationships between the soil properties and the concentrations of Cu in plants revealed a significant (P = 0.01) positive relationship (R² = 0.4) between organic carbon and the concentration of Cu in banana leaves. Aqua regia–extractable Cu was positively correlated (P = 0.03, R² = 0.4) with the concentrations of Cu in banana leaves. For bean leaves, electrical conductivity (EC) had a positive significant (P = 0.01) relationship (R² = 0.56) with the concentrations of Cu in the plants. It is recommended that further research be carried out to investigate the dynamics and bioavailability of Cu for the different crops interplanted in the coffee fields.     

Assessment of a laboratory method to obtain the equilibrium solution composition of forest soils

Equilibrium studies on soil require reliable estimates of ion concentrations in the soil solution under field conditions. We evaluated the previously described iterative method to approximate the equilibrium soil solution (ESS) with four acid forest soils. We examined for which ions the ESS is suitable, making use of the fact that concentrations in water extracts are functions of the soil: solution ratio. The electric conductivity, pH, and the concentrations of base cations, Mn²⁺, NO^?₃, SO₄²⁺, and dissolved organic carbon (DOC) were usually linear with the soil:solution ratio in water extracts, whereas no relation was observed for Al (with one exception) and Fe. Assuming that the ESS can be attributed the soil solution ratio of the field moist soil at the time of sampling, concentrations appeared as the continuation of the linear relation with the soil: solution ratio for base cations, pH, and the electric conductivity. This indicates that the ESS actually represents field conditions for these solution properties. For Al water extracts allowed no evaluation of the ESS result. The ESS underestimated SO₄^2? concentrations under field conditions, presumably because the lack of DOC in the solutions added distorts the balance amongst anions.