Prediction of zinc, cadmium, lead, and copper availability to wheat in contaminated soils using chemical speciation, diffusive gradients in thin films, extraction, and isotopic dilution techniques

To predict the availability of metals to plants, it is important to understand both solution- and solid-phase processes in the soil, including the kinetics of metal release from its binding agent (ligand and/or particle). The present study examined the speciation and availability of Zn, Cd, Pb, and Cu in a range of well-equilibrated metal-contaminated soils from diverse sources using several techniques as a basis for predicting metal uptake by plants. Wheat (Triticum aestivum L.) was grown in 13 metal-contaminated soils and metal tissue concentrations (Zn, Cd, Pb, and Cu) in plant shoots were compared with total soil metal concentrations, total soluble metal, and free metal activities (pM2+) in soil pore waters, 0.01 M CaCl2-extractable metal concentrations, E values measured by isotope dilution, and effective metal concentrations, C(E), measured by diffusive gradients in thin films (DGT). In the DGT technique, ions are dynamically removed by their diffusion through a gel to a binding resin, while E values represent the isotopically exchangeable (labile) metal pools. Free metal activities (Zn2+, Cd2+, and Pb2+) in soil pore waters were determined using a Donnan dialysis technique. Plant Zn and Cd concentrations were highly related to C(E), while relationships for Zn and Cd with respect to the other measures of metals in the soils were generally lower, except for CaCl2-extractable Cd. These results suggest that the kinetically labile solid-phase pool of metal, which is included in the DGT measurement, played an important role in Zn and Cd uptake by wheat along with the labile metal in soil solution. Plant Pb concentrations were highly related to both soil pore water concentrations and C(E), indicating that supply from the solid phase may not be so important for Pb. Predictions of Cu uptake by wheat from these soils by the various measures of Cu were generally poor, except surprisingly for total Cu.     

Relationship between metal speciation in soil solution and metal adsorption at the root surface of ryegrass

The total metal content of the soil or total metal concentration in the soil solution is not always a good indicator for metal availability to plants. Therefore, several speciation techniques have been developed that measure a defined fraction of the total metal concentration in the soil solution. In this study the Donnan Membrane Technique (DMT) was used to measure free metal ion concentrations in CaCl(2) extractions (to mimic the soil solution, and to work under standardized conditions) of 10 different soils, whereas diffusive gradients in thin-films (DGT) and scanning chronopotentiometry (SCP) were used to measure the sum of free and labile metal concentrations in the CaCl(2) extracts. The DGT device was also exposed directly to the (wetted) soil (soil-DGT). The metal concentrations measured with the speciation techniques are related to the metal adsorption at the root surface of ryegrass (Lolium perenne L.), to be able to subsequently predict metal uptake. In most cases the metal adsorption related pH-dependently to the metal concentrations measured by DMT, SCP, and DGT in the CaCl(2) extract. However, the relationship between metal adsorption at the root surface and the metal concentrations measured by the soil-DGT was not-or only slightly-pH dependent. The correlations between metal adsorption at the root surface and metal speciation detected by different speciation techniques allow discussion about rate limiting steps in biouptake and the contribution of metal complexes to metal bioavailability.     

Hardwood seeding root and nutrient parameters for a model of nutrient uptake

Use of mechanistic models is an increasingly accepted way to evaluate complex processes. The Barber-Cushman model provides a means to simulate nutrient uptake once information on root system characteristics, nutrient uptake, and soil nutrient supply are developed. Objectives of this study were to determine during a growing season: (i) root growth for 1-yr-old black cherry (Prunus serotina Ehrh.), northern red oak (Quercus rubra L.), and red maple (Acer rubrum L.) seedlings; (ii) net plant increase in N, P, K, Ca, and Mg; (iii) soil solution and solid phase nutrient concentrations; and (iv) the influence of root growth and soil nutrient supply changes on nutrient uptake using the Barber-Cushman model. Seedlings were grown in pots containing A horizon soil from two forest sites. Measurements were made on five occasions during the growing season. Root growth averaged 41.5 cm d-1 for red maple compared with 28.0 and 16.7 cm d-1 for cherry and oak, respectively. Seventy-five percent of root growth occurred at the end of the growing season. Total plant N showed the greatest change (25-58%) due to soil source. Model simulations underestimated observed uptake by 31 to 99%. A clear relationship between soil solution nutrient concentration and plant uptake, an important assumption of the model, was not observed. Results indicate care will need to be exercised in the development and use of root growth and nutrient supply values in mechanistic models.     

Phosphorus desorption dynamics in soil and the link to a dynamic concept of bioavailability

Soils under intensive livestock farming and heavily fertilized with animal manure may have elevated soil phosphorus (P) contents. We determined P desorption kinetics in batch experiments using soils from a pot experiment where grass was cropped on a P-rich noncalcareous sandy soil without P addition, to lower the soil P content. A diffusion model was used to describe P desorption kinetics from a spherical aggregate. The model was calibrated with data from the batch experiments. Simulation results show that in the pot experiment, P desorption from the solid phase of the inner layers was initially far from equilibrium with the rest of the aggregate, but desorption came closer to equilibrium as the soil P content decreased further. A simple tool is presented, referred to as the dynamic bioavailability index (DBI), to determine whether kinetics of P desorption limits plant uptake. This tool is the dimensionless ratio of the modeled maximal diffusive flux from soil aggregates to solution and the plant uptake rate measured in the pot experiment. The DBI was initially much larger than one; the maximal possible P desorption rate exceeded the uptake rate, so uptake was not limited by desorption. The DBI stabilized at a value somewhat larger than one after a while, due to soil transport limitations. This decrease coincided with a large decrease of the P content in the grass to a value (far) below what is considered as optimal; the supply rate of P from soil to the root cannot meet the demand needed for optimal P uptake. The DBI could be seen as a promising onset to a new dynamic approach of bioavailability.     

Effect of chloride in soil solution on the plant availability of biosolid-borne cadmium

Increasing chloride (Cl) concentration in soil solution has been shown to increase cadmium (Cd) concentration in soil solution and Cd uptake by plants, when grown in phosphate fertilizer- or biosolid-amended soils. However, previous experiments did not distinguish between the effect of Cl on biosolid-borne Cd compared with soil-borne Cd inherited from previous fertilizer history. A factorial pot experiment was conducted with biosolid application rates of 0, 20, 40, and 80 g biosolids kg(-1) and Cl concentration in soil solution ranging from 1 to 160 mM Cl. The Cd uptake of wheat (Triticum aestivum L. cv. Halberd) was measured and major cations and anions in soil solution were determined. Cadmium speciation in soil solution was calculated using GEOCHEM-PC. The Cd concentration in plant shoots and soil solution increased with biosolid application rates up to 40 g kg(-1), but decreased slightly in the 80 g kg(-1) biosolid treatment. Across biosolid application rates, the Cd concentration in soil solution and plant shoots was positively correlated with the Cl concentration in soil solution. This suggests that biosolid-borne Cd is also mobilized by chloride ligands in soil solution. The soil solution CdCl+ activity correlated best with the Cd uptake of plants, although little of the variation in plant Cd concentrations was explained by activity of CdCl+ in higher sludge treatments. It was concluded that chlorocomplexation of Cd increased the phytoavailability of biosolid-borne Cd to a similar degree as soil (fertilizer) Cd. There was a nonlinear increase in plant uptake and solubility of Cd in biosolid-amended soils, with highest plant Cd found at the 40 g kg(-1) rate of biosolid application, and higher rates (80 g kg(-1)) producing lower plant Cd uptake and lower Cd solubility in soil. This is postulated to be a result of Cd retention by CaCO3 formed as a result of the high alkalinity induced by biosolid application.     

The possibility of in situ heavy metal decontamination of polluted soils using crops of metal-accumulating plants

The decontamination of soils and wastes polluted with heavy metals presents one of the most intractable problems for soil clean-up. Present technology relies upon metal extraction or immobilization processes, both of which are expensive and which remove all biological activity in the soil during decontamination. They may only be appropriate for small areas of valuable redevelopment land. In this paper the use of metal-accumulating plants is explored for the removal of metals from superficially-contaminated soils such as those resulting from the long-term application to land of metal-contaminated sewage sludges. Green remediation employs plants native to metalliferous soils with a capacity to bioaccumulate metals such as zinc and nickel to concentrations greater than 2% in the aerial plant dry matter (hyperaccumulators). Growing such plants under intensive crop conditions and harvesting the dry matter is proposed as a possible method of metal removal and for ‘polishing’ contaminated agricultural soils down to metal concentrations below statutory limits. Not only are the biological activity and physical structure of soils maintained but the technique is potentially cheap, visually unobtrusive and offers the possibility of biorecovery of metals. The limitations of the process are reviewed and the future requirements for the development of efficient phytoremediators are outlined.     

Availability of arsenic, copper, lead, thallium, and zinc to various vegetables grown in slag-contaminated soils

To anticipate a possible hazard resulting from the plant uptake of metals from slag-contaminated soils, it is useful to study whether vegetables exist that are able to mobilize a given metal in the slag to a larger proportion than in an uncontaminated control soil. For this purpose, we studied the soil to plant transfer of arsenic, copper, lead, thallium, and zinc by the vegetables bean (Phaseolus vulgaris L. 'dwarf bean Modus'), kohlrabi (Brassica oleracea var. gongylodes L.), mangold (Beta vulgaris var. macrorhiza ), lettuce (Lactuca sativa L. 'American gathering brown'), carrot (Daucus carota L. 'Rotin', 'Sperlings's'), and celery [Apium graveiolus var. dulce (Mill.) Pers.] from a control soil (Ap horizon of a Entisol) and from a contaminated soil (1:1 soil-slag mixtures). Two types of slags were used: an iron-rich residue from pyrite (FeS2) roasting and a residue from coal firing. The metal concentrations in the slags, soils, and plants were used to calculate for each metal and soil-slag mixture the plant-soil fractional concentration ratio (CRfractional,slag), that is, the concentration ratio of the metal that results only from the slag in the soil. With the exception of TI, the resulting values obtained for this quantity for As, Cu, Pb, and Zn and for all vegetables were significantly smaller than the corresponding plant-soil concentration ratios (CRcontrol soil) for the uncontaminated soil. The results demonstrate quantitatively that the ability of a plant to accumulate a given metal as observed for a control soil might not exist for a soil-slag mixture, and vice versa.     

A regional-scale study on the crop uptake of cadmium from sandy soils: measurement and modeling

Plant uptake is one of the major pathways by which cadmium (Cd) in soils enters the human food chain. This study was conducted to investigate the uptake of Cd by crops from soils within the wastewater irrigation area (WIA) of Braunschweig (Germany) and to develop a simple process-oriented model that is suited to predict Cd uptake at the regional scale. The sandy soils within the WIA (4300 ha) have received considerable loads of heavy metals by irrigation using municipal wastewater for up to 40 years. In 1998 and 1999, we sampled soil and plant material at 40 potato (Solanum tuberosum L.), 40 sugar beet (Beta vulgaris L.), and 32 winter wheat (Triticum aestivum L.) fields. In both years and for all three crops, we found close linear relationships between the Cd content of plant material and the Cd concentration in soil solution. For all three crops, we observed a trend of relatively increased Cd uptake in the year with the higher saturation deficit of the atmosphere. We interpret this to indicate that transpiration plays an important role in the Cd uptake of crops under the conditions of the WIA. In modeling the uptake of Cd by crops, we assume that uptake is proportional to mass flow, that is, the product of water transpired, Cd concentration in soil solution, and a plant-specific empirical parameter. The simulations agreed well with the observed Cd contents in crops. Our model explained between 66 and 87% of the observed variance.     

The effect of pH on metal accumulation in two Alyssum species

Nickel phytoextraction using hyperaccumulator plants offers a potential for profit while decontaminating soils. Although soil pH is considered a key factor in metal uptake by crops, little is known about soil pH effects on metal uptake by hyperaccumulator plants. Two Ni and Co hyperaccumulators, Alyssum murale and A. corsicum, were grown in Quarry muck (Terric Haplohemist) and Welland (Typic Epiaquoll) soils contaminated by a Ni refinery in Port Colborne, Ontario, Canada, and in the serpentine Brockman soil (Typic Xerochrepts) from Oregon, USA. Soils were acidified and limed to cover pH from strongly acidic to mildly alkaline. Alyssum grown in both industrially contaminated soils exhibited increased Ni concentration in shoots as soil pH increased despite a decrease in water-soluble soil Ni, opposite to that seen with agricultural crop plants. A small decrease in Alyssum shoot Ni concentration as soil pH increased was observed in the serpentine soil. The highest fraction of total soil Ni was phytoextracted from Quarry muck (6.3%), followed by Welland (4.7%), and Brockman (0.84%). Maximum Ni phytoextraction was achieved at pH 7.3, 7.7, and 6.4 in the Quarry, Welland, and Brockman soils, respectively. Cobalt concentrations in shoots increased with soil pH increase in the Quarry muck, but decreased in the Welland soil. Plants extracted 1.71, 0.83, and 0.05% of the total soil Co from Welland, Quarry, and Brockman, respectively. The differences in uptake pattern of Ni and Co by Alyssum from different soils and pH were probably related to the differences in organic matter and iron contents of the soils.     

蓖麻（Ric inus communist L.）对锰矿区土壤中重金属累积特性的研究

为探讨蓖麻（Ricinus communist L.）对锰矿区土壤生态修复及能源化利用潜力,将不同品种蓖麻湘蓖1号和淄蓖7号播种在锰尾矿库土壤上,进入生殖生长阶段时采收全株,测定栽植土壤及植株根、茎、叶中5种重金属元素含量。结果显示：土壤中Mn平均含量最高达7884.96 mg＆#183;kg-1,超过国家规定的土壤环境质量域级标准6.5倍;湘蓖1号不同器官的Mn浓度从高至低为根＆gt;叶＆gt;茎,淄蓖7号不同器官Mn含量叶＆gt;茎＆gt;根,其叶中Mn平均浓度最高为765.43 mg＆#183;kg-1,较湘蓖1号叶中的平均含量高出79.53%, Pb、Cu、Cr含量及叶/根比值均大于湘蓖1号;植株体内重金属含量与土壤中重金属浓度的相关分析表明,重金属的积累量和转移量,受到土壤中几种重金属元素的共同影响。结果说明：2个品种的蓖麻均可以作为锰矿区能源化修复利用,对重金属的吸收和转运在品种间存在差异,淄蓖7号地上部分对重金属的迁移能力强于湘蓖1号。     

Responses of a non N-limited forest plantation to the application of alkaline-stabilized dewatered dairy factory sludge

Amendment of forest soils with dewatered dairy factory sludge (DDFS), characterized by low heavy metal contents and high amounts of degradable C, can prevent the depletion of soil nutrients that results from intensive harvesting in forest plantations. However, this practice involves environmental risks when N supplies exceed the demand of plants or when the strong acidity of the soil favors the mobility of trace metals. These aspects were assessed in a young radiata pine plantation growing in a sandy, acidic, and organic N-rich soil for the 7 yr after application of a DDFS. The supply of limiting nutrients (mainly P, Mg, and Ca) provided by application of the DDFS, along with control of the ground vegetation, improved the nutritional status of the stand and led to increases in timber volume of more than 60 to 100%. Increases in soil inorganic N were observed during the first months after amendment. Data from soil incubation experiments revealed that some of the additional N was immobilized and, to a lesser extent, denitrified due to the readily available organic C content of the DDFS. Leaching and increased plant uptake of N were prevented by a combination of the latter processes and the low rate of nitrification. The strong acidity of the soil enhanced the availability of Mn and Zn to plants, although the maximum concentrations did not reach levels harmful to organisms. We conclude that although application of DDFS has positive effects on tree nutrition and growth and the environmental risks are low, repeated application may favor mobility of N and availability of heavy metals.     

施入城市生活垃圾堆肥对玉米植株重金属分布及土壤养分的影响

以玉米为供试作物,研究施入生活垃圾堆肥对土壤和玉米各器官重金属分布规律及对土壤养分的影响。结果表明：连续3年施肥,土壤速效养分的含量明显增加;土壤重金属呈现累积,但含量远远低于二级土壤标准（GB 15618—1995）;植株中重金属含量表现为根部〉茎秆〉叶片〉籽粒,Cd在植株根部富集,但未大量向其他部位转移,玉米植株地上部分重金属含量明显低于饲料卫生标准（GB 13078—2001）。由此推断,在短期内（3年）,年施入60 000 kg·hm^-2的垃圾堆肥能提高土壤肥力,且暂时不会引起土壤重金属污染,也不影响玉米植株的饲用;使用多年后应及时监测,以保证安全性。     

Enhancing phytoextraction: the effect of chemical soil manipulation on mobility, plant accumulation, and leaching of heavy metals

For heavy metal-contaminated agricultural land, low-cost, plant-based phytoextraction measures can be a key element for a new land management strategy. When agents are applied into the soil, the solubility of heavy metals and their subsequent accumulation by plants can be increased, and, therefore, phytoextraction enhanced. An overview is given of the state of the art of enhancing heavy metal solubility in soils, increasing the heavy metal accumulation of several high-biomass-yielding and metal-tolerant plants, and the effect of these measures on the risk of heavy metal leaching. Several organic as well as inorganic agents can effectively and specifically increase solubility and, therefore, accumulation of heavy metals by several plant species. Crops like willow (Salix viminalis L.), Indian mustard [Brassica juncea (L.) Czern.], corn (Zea mays L.), and sunflower (Helianthus annuus L.) show high tolerance to heavy metals and are, therefore, to a certain extent able to use the surpluses that originate from soil manipulation. More than 100-fold increases of lead concentrations in the biomass of crops were reported, when ethylenediaminetetraacetic acid (EDTA) was applied to contaminated soils. Uranium concentrations could be strongly increased when citric acid was applied. Cadmium and zinc concentrations could be enhanced by inorganic agents like elemental sulfur or ammonium sulfate. However, leaching of heavy metals due to increased mobility in soils cannot be excluded. Thus, implementation on the field scale must consider measures to minimize leaching. So, the application of more than 1 g EDTA kg(-1) becomes inefficient as lead concentration in crops is not enhanced and leaching rate increases. Moreover, for large-scale applications, agricultural measures as placement of agents, dosage splitting, the kind and amount of agents applied, and the soil properties are important factors governing plant growth, heavy metal concentrations, and leaching rates. Effective prevention of leaching, breeding of new plant material, and use of the contaminated biomass (e.g., as biofuels) will be crucial for the acceptance and the economic breakthrough of enhanced phytoextraction.     

Plant growth and uptake of mineral elements at an oily sludge landfarming site in Kuwait

Oily sludge landfarmed in Kuwait soil contains higher concentrations of certain elements than that of the untreated of, soil, e.g. S, Cu, Cr, Zn, Pb, Ni, Mo and V. The growth and elemental content of three different plants grown on a sandy soil previously treated with different concentrations of oily sludge were studied. Tested plants differed in their response to landfarmed oily sludge; ryegrass was the least affected followed by oats, then barley. Uptake of elements differed both qualitatively and quantitatively between test plants. In barley, Zn increased in plants cultivated in soil treated with oily sludge, whereas other metal concentrations were reduced or not affected, namely, Cu, Pb, Ni, V. The uptake of P was greater in plants grown on treated soil compared with those on untreated soil, whereas Na, Ca, K, were either reduced or unaffected. In oats, Zn, Ni, Cu, Pb, V, were not significantly changed. Uptakes of K, Ca, P, and Na in plants from treated soil were higher than that of the control. In ryegrass, heavy metal concentrations were either reduced or remained the same as that of the control. In all cases, concentrations of essential heavy metals and other true elements under investigation were still lower than the levels considered to be sufficient for micronutrients. Thus, the oily sludge was a source of certain micro-nutrients which were deficient in the sandy soil. Further, it appears that uptake and distribution of elements in plant tissues were both highly variable according to the plant, species, and the soil characteristics.     

Changes in the rhizosphere of metal-accumulating plants evidenced by chemical extractants

The plants Salix viminalis L. (common osier) and Thlaspi caerulescens J. Presl & C. Presl have been studied often because of their high potential to extract heavy metals from soils. The soil properties favoring this phytoextraction are not yet fully known. In this study we compared three frequently used single-extracting agents (NaNO3, diethylenetriaminepentaacetic acid [DTPA], and ethylenediaminetetra-acetic acid [EDTA]) with a sequential extraction procedure to describe changes in the different Cd, Cu, and Zn pools in the rhizosphere of S. viminalis and T. caerulescens grown on calcareous and acidic Swiss soils in a pot experiment. The sequential extraction was used to assess the chemical affinities of these heavy metals (HM) in the soil whereas the single extractants were used for estimating the bioavailable HM pools in the soils. Cadmium depletion in several pools was most apparent in the acidic soil, with a significant decrease observed in the NaNO3-, DTPA-, and EDTA-extractable fractions following T. caerulescens growth compared with control pots. The sequential extraction showed that most Cd extracted by the plant from the acidic soil originated from the organic pool, which implies that heavy metals bound to organic matter may constitute a significant part of the bioavailable Cd pool in soils. In the calcareous soil only a small amount of Cd was taken up by T. caerulescens, and this came mainly from the carbonate-bound fraction. This study shows that T. caerulescens, and to a lesser extent S. viminalis, can alter the heavy metal distribution in different soil pools within 90 d.     

Root growth and metal uptake in four grasses grown on zinc-contaminated soils

Depth and area of rooting are important to long-term survival of plants on metal-contaminated, steep-slope soils. We evaluated shoot and root growth and metal uptake of four cool-season grasses grown on a high-Zn soil in a greenhouse. A mixture of biosolids, fly ash, and burnt lime was placed either directly over a Zn-contaminated soil or over a clean, fine-grained topsoil and then the Zn-contaminated soil; the control was the clean topsoil. The grasses were 'Reliant' hard fescue (Festuca brevipila R. Tracey), 'Oahe' intermediate wheatgrass [Elytrigia intermedia (Host) Nevski subsp. intermedia], 'Ruebens' Canada bluegrass (Poa compressa L.), and 'K-31' tall fescue (Festuca arundinacea Schreb.). Root growth in the clean soil and biosolids corresponded to the characteristic rooting ability of each species, while rooting into the Zn-contaminated soil was related to the species' tolerance to Zn. While wheatgrass and tall fescue had the strongest root growth in the surface layers (0-5 cm) of clean soil or biosolids, wheatgrass roots were at least two times more dense than those of the other grasses in the second layer (5-27 cm) of Zn-contaminated soil. When grown over Zn-contaminated soil in the second layer, hard fescue (with 422 mg/kg Zn) was the only species not to have phytotoxic levels of Zn in shoots; tall fescue had the highest Zn uptake (1553 mg/kg). Thus, the best long-term survivors in high-Zn soils should be wheatgrass, due to its ability to root deeply into Zn-contaminated soils, and hard fescue, with its ability to effectively exclude toxic Zn uptake.     

Decontamination of water polluted by heavy metals with Taro (Colocasia esculenta) cultured in a hydroponic NFT system

The toxicity and bioaccumulation of two heavy metals—lead (Pb) and cadmium (Cd)—in a semi-aquatic plant, Colocasia esculenta (L. Schott), from a synthetic heavy metal solution were studied. Young plants of equal size were grown hydroponically in shallow raceways containing Hoagland medium amended with 20, 40, and 60 mg l^?1 of Pb and 2, 4, and 6 mg l^?1 of Cd. The medium containing heavy metals was allowed to flow through the raceways with a change in influent heavy metal solution on every 5th day. The experiment was continued for 20 days. A set of control raceways—one comprised of nutrient medium with heavy metal supplements, devoid of plants, and another with the plants and nutrient medium having no metal supplement—was also simultaneously run. Chlorosis in the leaves was the prominent toxicity symptom observed due to Pb and Cd on the test plants. A significant decrease in the relative growth, biomass productivity, and total chlorophyll content were noticed in the plants with an increase in concentration of metal supplement in the solution and exposure time. Both metals accumulated to higher concentrations in the roots than in shoots, suggesting that the metals were bound to the root cells and their translocation to the leaves was limited. The results of the 20-day-long experiments indicate that from a phytoremediation perspective, C. esculenta is a promising plant species for remediation of wastewater polluted with lower concentrations of Pb and Cd.     

Hydrophobicity of soil colloids and heavy metal mobilization: effects of drying

Drying of soil may increase the hydrophobicity of soil and affect the mobilization of colloids after re-wetting. Results of previous research suggest that colloid hydrophobicity is an important parameter in controlling the retention of colloids and colloid-associated substances in soils. We tested the hypothesis that air-drying of soil samples increases the hydrophobicity of water-dispersible colloids and whether air-drying affects the mobilization of colloid-associated heavy metals. We performed batch experiments with field-moist and air-dried (25 degrees C) soils from a former sewage farm (sandy loam), a municipal park (loamy sand), and a shooting range site (loamy sand with 25% C(org)). The filtered suspensions (<1.2 microm) were analyzed for concentrations of dissolved and colloidal organic C and heavy metals (Cu, Cd, Pb, Zn), average colloid size, zeta potential, and turbidity. The hydrophobicity of colloids was determined by their partitioning between a hydrophobic solid and a hydrophilic aqueous phase. Drying increased hydrophobicity of the solid phase but did not affect the hydrophobicity of the dispersed colloids. Drying decreased the amount of mobilized mineral and (organo-)mineral colloids in the sewage farm soils but increased the mobilization of organic colloids in the C-rich shooting range soil. Dried samples released less colloid-bound Cd and Zn than field-moist samples. Drying-induced mobilization of dissolved organic C caused a redistribution of Cu from the colloidal to the dissolved phase. We conclude that drying-induced colloid mobilization is not caused by a change in the physicochemical properties of the colloids. Therefore, it is likely that the mobilization of colloids in the field is caused by increasing shear forces or the disintegration of aggregates.     

Growth of alfalfa in sludge-amended soils and inoculated with rhizobia produced in sludge

The efficiency of rhizobial inoculants produced in wastewater sludge used as a growth medium and as a carrier was compared with that of inoculants produced in yeast mannitol broth (YMB) medium and by using peat as a carrier. Alfalfa (Medicago sativa L.) plants were inoculated with solid and liquid Sinorhizobium meliloti inoculants and grown in pots containing two soil types (Kamouraska clay soil and Saint-André sandy soil). The effect of various levels of sludge amendment (60 and 120 kg N/ha) and nitrogen fertilizer (60 kg N/ ha) was also studied. The sludge-based inoculants showed the same symbiotic efficiency (nodulation and plant yield) as YMB-based inoculants. The inoculation increased the nodulation indexes from 4-6 to 8-12, and the rhizobial number from 10(3) (uninoculated soils) to 10(6)-10(7) cells/g in inoculated soils. However, the shoot dry weights and the nitrogen contents were not increased significantly by the inoculation. Applying sludge as an amendment enhanced the rhizobial number in soils from 10(3) to 10(4) cells/g and improved significantly the plant growth (shoot dry weights and nitrogen contents). This improvement increased with sludge rate and with the cut (three cuts). Compared with sludge, N fertilizer gave lower plant yields. The nodulation was not affected by sludge and N-fertilizer application. The texture and physico-chemical properties of soil were found to affect the yield and nitrogen content of the plants. In this study, macroelements and heavy metals were at acceptable levels and were not considered to be negative factors.     

Copper and zinc bioavailabilities to ryegrass (Lolium perenne L.) and subterranean clover (Trifolium subterraneum L.) grown in biosolid treated Chilean soils

The purpose of this study was assessing Cu and Zn availabilities in soils amended with a biosolid through the determination of their sequentially extracted chemical forms and their relationship with the contents of these metals in ryegrass (Lolium perenne L.) and subterranean clover (Trifolium subterraneum L.) plant tissues cultivated in a greenhouse using four soils classified as Aquic Xerochrepts and Ultic Haploxeralfs representatives of potential areas for biosolids application in the central zone of Chile. The soils were treated with sewage sludge at a rate of 0 and 30 Mg ha⁻¹. The greenhouse experiment was carried out through a completely randomized block design in a 2 × 4 (biosolid rate × soil) arrangement, considering three repetitions per treatment. The soils used in the greenhouse experiment before and after cultivation, were sequentially extracted with specific reagents and conditions in order to obtain the following fractions: exchangeable, sodium acetate-soluble, soluble in moderately reducing condition, K₄P₂O₇-soluble, soluble in reducing condition, and soluble in strongly acid and oxidizing condition. It was established that Cu and Zn were predominantly found in soils in less available forms, associated to organic matter, oxides and clay minerals. Zinc concentration in ryegrass plants was higher than that found in subterranean clover plants in biosolid-amended soils. Zinc contents in ryegrass shoot and root correlated with the exchangeable, bound-to-carbonate, and bound-to-FeOx metal forms in control soil. Copper and Zn bioavailabilities were estimated through satisfactorily fitted multiple linear regression models, with determination coefficients from 0.77 to 0.99, which showed a positive contribution of the labile metal forms in soils, especially in relation to Zn in both plant species.