Sugarecane molasse and vinasse added as microbial growth substrates increase calcium carbonate content, surface stability and resistance against wind erosion of desert soils.

Wind erosion is one of the main factors of soil degradation and air pollution in arid and semi-arid regions. In this study we evaluated microbial-induced carbonate precipitation (MICP) as an alternative soil conservation method against wind erosion using sugar cane molasse and vinasse as growth substrates in comparison to tryptic soy broth (TSB). The three substrates were applied in laboratory tests with and without addition of MICP cementing solution (1 M urea plus calcium chloride) to two sandy soils differing in calcium carbonate content. The performance of MICP solution inoculated with a cultured urease-producing strain of Sporosarcina pasteurii was compared to that of an autoclaved MICP solution. For control we also performed a blank treatment without substrate, MICP solution and inoculation. In addition to lab tests in which we determined the effects of treatments on soil pH, electrical conductivity (EC), calcium carbonate (CaCO3) content and surface penetration resistance, we performed wind tunnel experiments to determine soil loss by deflation under different wind velocities. Applying vinasse and molasse strongly increased soil CaCO3 content and penetration resistance, with and without addition of inoculated or non-inoculated MICP solution. Vinasse generally had stronger effects than molasse, while TSB was less effective, especially on penetration resistance. The addition of MICP solution in most treatments did not enhance but rather decrease the substrate effects. In the treatments with vinasse and molasse, increase in penetration resistance translated into substantially decreased soil loss in the wind tunnel tests, down to around one third of the loss in the blank treatment. In contrast, soil loss substantially increased in the treatments with TSB, probably due to the high input of sodium with this substrate. Our results show that molasse and, even more, vinasse can have a strong soil stabilization effect against wind erosion, which is primarily related to the formation of CaCO3 content and does not depend on additional amendments. Thus, these substrates have a great potential to be used on their own as environmentally friendly and cost-effective amendments to control wind erosion of bare sandy soils in arid environments.

Soil cadmium uptake by cocoa in Honduras.

Cadmium (Cd) is a trace metal without essential biological functions that is toxic to plants, animals and humans at low concentrations. It occurs naturally in soils, but inputs from anthropogenic sources have increased soil Cd contents worldwide. Cadmium uptake by cocoa (Theobroma cacao L.) has recently attracted attention, after the European Union (EU) decided to bring into force values for maximum Cd concentrations in cocoa products that would be exceeded by current products of various provenances from Latin America. In order to identify factors governing Cd uptake by cocoa, we carried out a survey on 55 cocoa farms in Honduras in which we determined Cd concentrations in cocoa leaves, pod husks and beans and analysed their relationships to a variety of surrounding soil and site factors. Averaging 2.6±0.4mgkg-1, the concentrations of Cd were higher in the leaves than in the beans. With an average of 1.1±0.2mgkg-1, the bean Cd concentrations still exceeded the proposed EU limit, however. The bean Cd showed large differences between geological substrates, even though regional variations in 'total' soil Cd were comparably small and the average concentration was in the range of uncontaminated soils (0.25±0.02mgkg-1). As we found no influence of fertilizer application or vicinity to industrial sites, we conclude that the differences in soil Cd between sites were due to natural variation. Of all factors included here, DGT-available soil Cd was the best predictor of bean Cd (R2=0.5). When DGT was not considered, bean Cd was best predicted by 'total' soil Cd, pH and geology. The highest bean Cd concentrations were found on alluvial substrates.

Cadmium uptake by cocoa trees in agroforestry and monoculture systems under conventional and organic management.

Cadmium (Cd) uptake by cocoa has recently attracted attention, after the European Union (EU) decided to establish values for tolerable Cd concentrations in cocoa products. Bean Cd concentrations from some cocoa provenances, especially from Latin America, were found to exceed these values. Cadmium uptake by cocoa is expected not only to depend on a variety of soil factors, but also on plant and management factors. In this study, we investigated the influence of different production systems on Cd uptake by cocoa in a long-term field trial in the Alto Beni Region of Bolivia, where cocoa trees are grown in monocultures and in agroforestry systems, both under organic and conventional management. Leaf, fruits and roots of two cultivars were sampled from each production system along with soil samples collected around these trees. Leaf, pod husk and bean samples were analysed for Cd, iron (Fe) and zinc (Zn), the roots for mycorrhizal abundance and the soil samples for 'total' and 'available' Cd, Fe and Zn as well as DGT-available Cd and Zn, pH, organic matter, texture, 'available' phosphorus (P) and potassium (K). Only a small part of the variance in bean and pod husk Cd was explained by management, soil and plant factors. Furthermore, the production systems and cultivars alone had no significant influence on leaf Cd. However, we found lower Cd leaf contents in agroforestry systems than in monocultures when analysed in combination with DGT-available soil Cd, cocoa cultivar and soil organic matter. Overall, this model explained 60% of the variance of the leaf Cd concentrations. We explain lower leaf Cd concentrations in agroforestry systems by competition for Cd uptake with other plants. The cultivar effect may be explained by cultivar specific uptake capacities or by a growth effect translating into different uptake rates, as the cultivars were of different size.

Fate and movement of selenium from drainage sediments disposed onto soil with and without vegetation.

Disposal options for salty and selenium-laden agricultural drainage sediments are needed to protect the agricultural ecosystem in Central California. Thus, a 7-year pilot-scale field study evaluated the effects of disposing Se-laden drainage sediment onto soil that was planted with either salado grass (Sporobolus airoides 'salado') or cordgrass (Spartina patens 'Flageo'), or on soil left bare with and without irrigation. Significant decreases in salinity and water-extractable and total soil Se concentrations were observed in all treatments to a depth 30 cm, while water extractable Se and salinity increased most significantly between 30 and 60 cm. Total yields increased over time for both species, while plant Se concentrations were ≈10 and 12 mg kg(-1) DM for salado and cordgrass, respectively. The results show that Se and soluble salts disposed of as Se-laden drainage sediment onto light textured soils will significantly migrate to lower depths with or without vegetation.

Nitrogen dynamics in oak model ecosystems subjected to air warming and drought on two different soils.

Being tolerant to heat and drought, oaks are promising candidates for future forestry in view of climate change in Central Europe. Air warming is expected to increase, and drought decrease soil N availability and thus N supply to trees. Here, we conducted a model ecosystem experiment, in which mixed stands of young oaks (Quercus robur, Q. petraea and Q. pubescens) were grown on two different soils and subjected to four climate treatments during three growing seasons: air warming by 1-2 °C, drought periods (average precipitation reduction of 43-60%), a combination of these two treatments, and a control. In contrast to our hypotheses, neither air warming nor drought significantly affected N availability, whereas total amounts, vertical distribution and availability of soil N showed substantial differences between the two soils. While air warming had no effect on tree growth and N accumulation, the drought treatment reduced tree growth and increased, or tended to increase, N accumulation in the reduced biomass, indicating that growth was not limited by N. Furthermore, (15) N-labelling revealed that this accumulation was associated with an increased uptake of nitrate. On the basis of our results, climate change effects on N dynamics are expected to be less important in oak stands than reduced soil water availability.

Water regime and growth of young oak stands subjected to air-warming and drought on two different forest soils in a model ecosystem experiment.

Global climate change is expected to increase annual temperatures and decrease summer precipitation in Central Europe. Little is known of how forests respond to the interaction of these climate factors and if their responses depend on soil conditions. In a 3-year lysimeter experiment, we investigated the growth response of young mixed oak stands, on either acidic or calcareous soil, to soil water regime, air-warming and drought treatments corresponding to an intermediate climate change scenario. The air-warming and drought treatments were applied separately as well as in combination. The air-warming treatment had no effect on soil water availability, evapotranspiration or stand biomass. Decreased evapotranspiration from the drought-exposed stands led to significantly higher air and soil temperatures, which were attributed to impaired transpirational cooling. Water limitation significantly reduced the stand foliage, shoot and root biomass as droughts were severe, as shown in low leaf water potentials. Additional air warming did not enhance the drought effects on evapotranspiration and biomass, although more negative leaf water potentials were observed. After re-watering, evapotranspiration increased within a few days to pre-drought levels. Stands not subjected to the drought treatment produced significantly less biomass on the calcareous soil than on the acidic soil, probably due to P or Mn limitation. There was no difference in biomass and water regime between the two soils under drought conditions, indicating that nutrient availability was governed by water availability under these conditions. The results demonstrate that young oak stands can cope with severe drought and therefore can be considered for future forestry.

Effects of three amendments on extractability and fractionation of Pb, Cu, Ni and Sb in two shooting range soils.

Contamination of shooting range soils with toxic trace elements, in particular Pb and Sb, is of increasing environmental concern worldwide. We studied the extractability of Sb, and other metals in two shooting range soils: a calcareous soil (pH 8) with low organic carbon (0.5%) and a non-calcareous soil (pH 6.3) with elevated organic carbon content (5%). Both soils contained total concentrations of around 500 mg kg(-1) Pb, 65 mg kg(-1) Cu, 100 mg kg(-1) Zn and 20 mg kg(-1) Sb. We tested the effects of Ca(OH)(2), phosphate and sodium humate amendments on metals and Sb extractability. Extracts with H(2)O and NaNO(3) contained 0.02-0.05% of the total Zn and Pb; 0.1-0.5% of total Ni and Cu and approximately 1% of total Sb. Sequential extraction procedure of Zeien and Brümmer resulted in similar percentages for the sum of the two most labile fractions (F1+F2) in two soils: 10% Pb, and 15-20% Sb. Water and NaNO(3)-extractable Sb concentrations increased after phosphate addition, but were not affected by the addition of sodium humate. The results show that leaching of Sb from shooting ranges into ground and surface waters may generate a serious environmental risk under widely different soils conditions.

Metal solubility and speciation in the rhizosphere of Lupinus albus cluster roots.

The objective of this study was to investigate the influence of root exudation of organic acid anions on the speciation of major and trace metal cations in the rhizosphere of Lupinus albus cluster roots. Plants were grown in rhizoboxes containing repacked weakly acidic loam. Bulk soil solutions and, during the lifetime of cluster roots, rhizosphere solutions were collected using micro suction cups. During organic acid anion exudation bursts, metals in the rhizosphere of cluster roots were strongly mobilized. The concentrations of dissolved organic carbon derived from soil organic matter increased parallel to organic acid anions. Speciation calculations revealed that, during exudation, Al, Ca, Mn, and Zn in the cluster root rhizosphere were mainly bound with citrate, while Cu and Pb were always strongly bound to soil-derived dissolved organic matter. Our results indicate that cluster root exudation led on one hand to direct mobilization and complexation of metals like Al, Fe, and Zn by citrate and on the other hand to the mobilization of soil organic matter which complexes and solubilizes Cu and Pb.

Uptake of Zn and Fe by wheat (Triticum aestivum var. Greina) and transfer to the grains in the presence of chelating agents (ethylenediaminedisuccinic acid and ethylenediaminetetraacetic acid).

A way to decrease iron and zinc deficiency in humans is to biofortify foods by increasing the bioavailable contents in these elements. The aim of this work was to study if chelating agents could be used to increase the capture of Fe and Zn by wheat grains. Zn and/or Fe in combination with the chelating agents ethylenediaminedisuccinic acid (EDDS) or ethylenediaminetetraacetic acid (EDTA) were added at various times (i.e., at flower head formation, anthesis, and postanthesis) to spring wheat ( Triticum aestivum var. Greina) grown in nutrient solution. Treatments lasted for 2 weeks, and the plants were harvested at grain maturity. The shoots of treated plants accumulated higher Zn and/or Fe concentrations than untreated plants, depending on the treatment. The plants also accumulated significant concentrations of EDDS or EDTA in their shoots. Elevated Zn and Fe concentrations in the shoots did in most cases not lead to significantly higher Zn and Fe concentrations in the grains. The grains of plants treated with EDDS during flower head formation accumulated elevated Fe and Zn concentrations but at the cost of a reduction in yield. The control plants transferred higher percentages of Fe and Zn from the shoot into the grain than the treated plants. This indicates that EDTA and EDDS inhibited in most cases the translocation of Fe and Zn from the shoots into the grains. The amounts of EDDS and EDTA found in the grains of treated plants were very small. This indicates that there was little transfer of the chelates into the symplast and that the apoplastic pathway, which is important for the transport of chelants into the shoots, is efficiently blocked between shoots and seeds.

Changes in lead availability affect bacterial community structure but not basal respiration in a microcosm study with forest soils.

This study investigates the effects of Pb during time on the bacterial communities of forest soils using water-extractable Pb concentrations in the soil solution as predictors of Pb bioavailability. In a microcosm experiment we applied increasing concentrations of Pb(NO(3))(2) solutions (0.5, 2, 8, 32 mM) to 5 forest soils of pH<5 and to a calcareous soil of pH>6.5. Sampling of the microcosms was performed after 3, 30 and 90 days of incubation. Community analysis included basal respiration rates and changes in the structure of the bacterial communities through T-RFLP fingerprinting. We also investigated functional stability in terms of resistance, expressed as the effects on basal respiration after 3 days of incubation, and of resilience, expressed as the recovery of bacterial community structure and of respiration rates after 90 days of incubation. Water-extractable Pb increased with time in most of the soils, in parallel with an increase of water-extractable dissolved organic carbon (DOC). The increased concentrations slightly affected bacterial community structure, although OTU (operational taxonomic unit) richness was not significantly reduced with Pb concentrations in any of the soils. The highest Pb treatment (32 mM) caused significant effects on basal respiration in some of the acidic soils, but no clear trend was observed in relation to increased Pb bioavailability with time. Resistance to Pb additions was evident in five of the six soils, but only two showed resilience after 90 days. This is the first study showing the effects of time on Pb bioavailability in soils and on the resulting reactions of the soil microbial communities.

Determination of [S,S']-ethylenediaminedisuccinic acid by high-performance liquid chromatography.

A new high-performance liquid chromatography (HPLC) method for the determination of ethylenediaminedisuccinic acid (EDDS) is presented. Free EDDS(4-) and EDDS complexes with divalent metals undergo conversion to the Fe(III) complex in the presence of Fe(III)Cl(3). Fe(III)EDDS is separated by HPLC on an ion exchange column using (NH(4))(2)SO(4) eluent with detection at 258 nm. The detection limit is 0.01 microM. The method is applied to natural waters and soil solution samples. A background of natural water results in a reduction in EDDS peak area. The method is suited for EDDS analysis in samples with well-defined, simple matrices such as those used in laboratory experiments or biodegradation studies.

Sorption of trace metals by standard and micro suction cups in the absence and presence of dissolved organic carbon.

Both the bioavailability of a trace metal (TM) in a soil and the risk of leaching to the ground water are linked to the metals concentration in the soil solution. Sampling soil solution by tension lysimetry with suction cups is a simple and established technique that is increasingly used for monitoring dissolved TM in soils. Of major concern, however, is the sorption of TM by the walls of the samplers. Metal sorption by different materials used in suction cups can vary widely, depending also on the chemistry of the soil solution. We compared the sorption of Cu, Zn, Cd, and Pb by different standard-size and micro suction cups in the laboratory at two pH values (4.5 and 7.5 or 8.0) in absence and presence of dissolved organic carbon (DOC). In addition, we investigated the sorption of DOC from different origins by the cup materials. At both pH values, the weakest sorption of all four TMs was exhibited by standard-size suction cups based on nylon membranes and by hollow fibers made from polyvinyl alcohol (PVA). At alkaline pH, borosilicate glass, ceramic materials, and polytetrafluorethylene (PTFE) mixed with silicate were characterized by generally strong sorption of all investigated TMs. In addition, Cu and Pb were strongly sorbed at low pH by PTFE-silicate and a ceramic material used for the construction of standard-size suction cups. On the other hand, sorption of Cu, Zn, and Cd by ceramic capillaries produced from pure aluminum oxide was negligible at low pH. Micro suction cups made of an unknown polymerous tube sorbed Cu strongly, but were well suited to monitor Zn, Cd, and Pb at low pH, and, in the presence of DOC, also at high pH. Major cations (Na+, Mg2+, K+, Ca2+) and anions (Cl-, NO3-, SO4(2-)) were not or very weakly sorbed by all cup materials, except for Mg2+, K+, and Ca2+ by borosilicate glass at pH 7.5. Trace metal sorption by suction cups was generally greatly reduced in the presence of DOC, especially at alkaline pH. The sorption of DOC itself depended on its source. Dissolved organic carbon from leaf litter extracts with a probably large hydrophobic fraction was sorbed more strongly than mainly hydrophilic DOC from a mineral soil solution.

Effect of corn root exudates on the degradation of atrazine and its chlorinated metabolites in soils.

DIMBOA (3,4-dihydro-2,4-dihydroxy-7-methoxy-2H-1,4-benzoxazin-3-one), a major benzoxazinone of Poaceae plants, was isolated and purified from corn seedlings. The effect of isolated and purified DIMBOA on the degradation of atrazine [2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine], and its toxic breakdown products, desethylatrazine [2-chloro-4-amino-6-(isopropylamino)-s-triazine; DEA] and desisopropylatrazine [2-chloro-4-(ethylamino)-6-amino-s-triazine; DIA], was studied in the absence of plants using batch experiments, while the effect of corn root exudates on these compounds was determined in hydroponic experiments. Degradation experiments were performed in the presence and absence of 50 microM, 1 mM, or 5 mM DIMBOA resulting in ratios of DIMBOA to pesticide of 1:1, 20:1, and 100:1. We observed a 100% degradation of atrazine to hydroxyatrazine within 48 h at a ratio of DIMBOA to atrazine of 100:1. DIMBOA had the largest effect on atrazine, while it was about three times less effective on DEA and DIA. Corn (Zea mays L. cv. LG 2185) was exposed to 10 mg L(-1) of either atrazine, DEA, or DIA for 11 d in a growth chamber experiment. Up to 4.3 micromol L(-1) d(-1) of hydroxyatrazine were formed in the nutrient solutions by plants exposed to atrazine, while the formation of hydroxylated metabolites from plants exposed to DEA and DIA was smaller and also delayed. The formation of hydroxylated metabolites increased in the solution with plant age in all atrazine, DEA, and DIA treatments. HMBOA (3,4-dihydro-2-hydroxy-7-methoxy-2H-1,4-benzoxazin-3-one), the lactam precursor of DIMBOA, and a tentatively identified derivative of MBOA (2,3-dihydro-6-methoxy-benzoxazol-2-one) were detected in the corn root exudates. Mass balance calculations revealed that up to 30% of the disappearance of atrazine and DEA, and up to 10% of DIA removal from the solution medium in our study could be explained by the formation of hydroxylated metabolites in the solution itself. Our results show that higher plants such as corn have the potential to promote the hydrolysis of triazine residues in soils by exudation of benzoxazinones.

Mapping risk of cadmium and lead contamination to human health in soils of Central Iran.

In order to map Cd and Pb contamination in the soils of the region of Isfahan, Central Iran, we performed indicator kriging on a set of 255 topsoil samples (0-20 cm) gathered irregularly from an area of 6800 km(2). The measured Cd concentrations exceeded the Swiss guide value in more than 80% of the samples whereas Pb concentrations exceeded the respective guide value only in 2% of the samples. Based on the simulated conditional distribution functions, the probability of exceeding the concentration of Cd and Pb from the specific threshold was computed. The results indicated that in most parts of the region the probability of contamination by Cd is very large (>0.95) whereas it is small (<0.5) for Pb. Based on a misclassification analysis, we chose the probability of 0.45 as optimum probability threshold to delineate the polluted from unpolluted areas for Cd. In addition, we performed a loss analysis to separate risks to human health from potential losses due to remediation costs. Based on this analysis a probability threshold of 0.8 was found to be the optimum threshold for the classification of polluted and unpolluted areas in the case of Cd. Health risks were found to be larger in the western parts of the region. Misclassification analysis was sufficient for risk mapping for Pb as its concentration did not reach risk levels for human health. A probability of 0.7 for Pb was found to be the optimum threshold for the delineation of polluted and unpolluted lands.

The role of nitrilotriacetate in copper uptake by tobacco.

In growth chamber experiments we studied the effect of nitrilotriacetate (NTA) on Cu uptake by tobacco (Nicotiana tabacum L.). Plants were exposed for 6 d to 126 microM Cu and 500 microM NTA in nutrient solutions without and with 10 g L(-1) montmorillonite. Approximately seven times less Cu was dissolved in the montmorillonite solutions than in the nutrient solutions alone. In the absence of NTA, montmorillonite effectively competed with plant roots for Cu, although Cu remained bound to the roots. Nitrilotriacetate increased Cu uptake and translocation into shoots of tobacco by a factor of 3.5 from the nutrient solution and by a factor of 26 from the montmorillonite nutrient solution. Neither growth reduction nor any other visible sign of Cu toxicity was found in the presence of NTA with Cu concentrations of 190 mg kg(-1) in the shoots. In the absence of NTA, high Cu concentrations in root samples led to a brownish discoloration of the roots.

Assessment of uncertainty and risk in modeling regional heavy-metal accumulation in agricultural soils.

Present agricultural land use and atmospheric deposition may lead to heavy-metal accumulation rates in soils that may violate soil quality standards in the future. To undertake suitable preventive measures against heavy-metal enrichment, flux balances in agroecosystems and their uncertainties have to be assessed. For this reason we developed an empirical stochastic model, PROTERRA-S, that considers heavy-metal inputs through agricultural management as well as outputs by crop removal and leaching on a regional scale. In this manuscript we describe application of PROTERRA-S to the Sundgau region in Switzerland. Considering uncertainty in informational and natural variability, large variations of the aggregated regional cadmium and zinc balances were found, with standard deviations that were of the same order of magnitude as their average values. Uncertainty in the simulated net zinc flux originated mainly from uncertainty in the zinc concentrations of manure and crops and from uncertainty in atmospheric deposition of zinc. For cadmium, the main contribution to the total uncertainty came from uncertainty in crop concentration, regression functions to estimate Freundlich parameters, atmospheric deposition, and from spatial variation of soil pH and cation exchange capacity (CEC). For both zinc and cadmium, informational uncertainty in input data were large, indicating that significant uncertainty reduction could be achieved by additional data collection campaigns. A monetary risk value for the regional zinc accumulation rate in Sundgau was calculated to be on the order of 22 million Euro.

Influence of clay minerals on the hydrolysis of carbamate pesticides.

Using batch experiments, we investigated the influence of clay minerals (montmorillonite, beidellite, illite, and vermiculite) on the hydrolysis of five carbamate pesticides: carbosulfan, carbofuran, aldicarb, pirimicarb, and chlorpropham. Compared to the other minerals, montmorillonite had the strongest influence on the hydrolysis of these carbamates. Montmorillonite enhanced the hydrolysis of carbosulfan and aldicarb. In contrast, the hydrolysis of chlorpropham was inhibited by montmorillonite, probably because of its strong adsorption on montmorillonite. The hydrolysis of pirimicarb was not affected by montmorillonite. The presence of organic substances, phosphate, and fluoride in suspensions decreased the catalytic activity of montmorillonite. Surface acidity of montmorillonite and/or formation of surface chelates are probably the key factors of surface catalysis in the case of the hydrolysis of carbosulfan.

Elevated lead and zinc contents in remote alpine soils of the Swiss National Park.

Weathering of bedrock and pedogenic processes can result in elevated heavy metal concentrations in the soil. Small-scale variations in bedrock composition can therefore cause local variations in the metal content of the soil. Such a case was found in the remote alpine area of the Swiss National Park. Soil profiles were sampled at an altitude of about 2,400 m, representing soils developed above different bedrocks. The concentration of lead in the profiles was found to be strongly dependent on the metal content in the bedrock underlying the soil and was strongly enriched in the top 10 cm. The dolomitic bedrock in the study area contains elevated lead concentrations compared with other dolomites. Dissolution of dolomite and accumulation of weathering residues during soil formation resulted in high lead concentrations throughout the soil profile. The enrichment of lead in the topsoil, however, is largely attributed to atmospheric input. The isotopic signature of the lead clearly indicates that it is mainly of natural origin and that atmospheric deposition of anthropogenic lead contributed to about 20 to 40% to the lead concentration in the topsoil on the bedrock with elevated lead concentrations. In the soils on bedrock with normal lead concentrations, the anthropogenic contribution is estimated to be about 75%. Also, zinc was very strongly enriched in the topsoil. This enrichment was closely correlated with the organic matter distribution in the profiles, suggesting that recycling through plant uptake and litter deposition was a dominant process in the long-term retention of this metal in the soil.

A stochastic empirical model for regional heavy-metal balances in agroecosystems.

Mass flux balancing provides essential information for preventive strategies against heavy-metal accumulation in agricultural soils that may result from atmospheric deposition and application of fertilizers and pesticides. In this paper we present the empirical stochastic balance model, PROTERRA-S, that estimates heavy-metal and phosphorus accumulation in agricultural soils on the regional level. The basic units of these balances are land use systems defined by livestock production and cultivated crops. The model is designed to use available databases, such as regional agricultural statistics and soil information systems. In a case study, we assessed the phosphorus, cadmium, and zinc balances for the Sundgau region, Switzerland. The regional P requirements of crops were mainly supplied by animal manure (56%) and commercial fertilizers (40%). Net cadmium fluxes of the land use systems ranged from 1.0 g ha(-1) yr(-1) (dairy and mixed farm types) to 17.8 g ha(-1) yr(-1) (animal husbandry systems), whereas the regional net cadmium flux was only 1.4 g ha(-1) yr(-1). The regional net zinc flux was 605 g ha(-1) yr(-1). The smallest net zinc flux of 101 g ha(-1) yr(-1) was found for an arable farm type, whereas for animal husbandry systems fluxes up to 39.8 kg ha(-1) yr(-1) were estimated. Comparison of model results with reported metal balances of experimental farms shows that identification of agricultural land with high risks of heavy-metal accumulation benefits from stratification of heavy-metal balances according to land use systems while accounting for their P fertilization plans. Consequently, the model may support sustainable management of heavy-metal cycles in agricultural soils.

Heavy metal effects on beta-glucosidase activity influenced by pH and buffer systems.

Inhibition of beta-glucosidase activity by Cu(II), Zn(II) and Ni(II) was investigated as a function of pH and buffer type. Both factors were found to exert a strong effect on the activity of the enzyme. All three of the investigated heavy metals inhibited the enzyme activity in acetate buffer. At metal concentrations of 0.6 mM, Zn and Ni reduced the enzyme activity by 25-30% under optimal pH conditions (pH 5-5.2). Under the same conditions, Cu showed an even more pronounced inhibitory effect than Zn and Ni. In presence of 0.6 mM Cu, the enzyme activity was lowered by more than 90% in comparison to metal free systems. In contrast to these results, no enzyme inhibition was observed in citrate buffer, even in the presence of 1 mM Cu. The inhibition of beta-glucosidase activity by Cu increased with increasing pH. Inhibition by Zn and Ni was less pH-dependent in the observed pH range (pH 4-5.5). Copper caused a distinct shift in the pH optimum of enzyme activity, whereas this was not the case for Zn or Ni. The effects of buffer and pH on enzyme inhibition by Cu, Zn and Ni were successfully described using a chemical speciation model, based on the assumption that enzyme activity depends on the protonation of the amino acids at the reactive site and that enzyme activity is inhibited by complexation of the reactive sites by the heavy metal cations. The results show the importance of taking chemical conditions and speciation into account when investigating the effect of heavy metal cations on biological systems.