Soil‐ecological evaluation of willows in a floodplain

Willows (Salix spp.) were supposed to be suitable candidates for the phytoremediation of polluted floodplain soils, but it is unknown how willow growth alters concentrations and mobility of pollutants under the conditions of ongoing periodically flooding. Therefore, effects of willow cropping on total concentrations and mobility of As and heavy metals and soil microbial properties were determined after three and four growing seasons under willows in comparison to native grassland in a flood channel of a River Elbe floodplain (Central Germany). After 4 y of willow coppice, the heavy metal concentrations (mg kg^–1) were increased not only in the grass control plots (final Cu 274, Pb 276, Zn 935) but also under the willows (final Cu 248, Pb 251, Zn 779) compared to the initial concentrations (initial Cu 170, Pb 156, Zn 579). This increase might likely be caused by the ongoing sedimentation by flood events. The smaller increase under willows compared to grass might be related to an initial net effect of phytoextraction. The concentrations of the mobile fractions of Cd, Cu, Ni, and Zn were significantly lower under willows than under grass. Higher β‐glucosidase activities under willows than under grass might indicate a starting net decomposition of organic matter. Therefore, the study of long‐term and large‐scale effects are recommend before an appropriate evaluation of willow short‐rotation coppice for phytoremediation of polluted floodplains will be established.     

Heavy‐metal displacement in chelate‐treated soil with sludge during phytoremediation

Heavy metals (HMs) in domestic sewage sludge, applied to land, contaminate soils. Phytoremediation is the use of plants to clean‐up toxic HMs from soil. Chelating agents are added to soil to solubilize the metals for enhanced uptake. Yet no studies report the displacement of HMs in soil with sludge following solubilization with chelates. The objective of this work was to determine the uptake or leaching of HMs due to a chelate added to a soil from a sludge farm that had received sludge for 25 y. The soil was placed in long columns (105 cm long; ?? 39 cm) in a greenhouse. Columns either had a plant (hybrid poplar; Populus deltoides Marsh. × P. nigra L.) or no plant. After the poplar seedlings had grown for 144 d, the tetrasodium salt of the chelating agent EDTA was irrigated onto the surface of the soil at a rate of 1 g per kg of soil. Drainage water, soil, and plants were analyzed for three toxic HMs (Cd, Ni, Pb) and four essential HMs (Cu, Fe, Mn, Zn). At harvest, extractable and total concentrations of each HM in the soil with EDTA were similar to those in soil without EDTA. The chelate did not affect the concentrations of HMs in the roots or leaves. With or without plants, EDTA mobilized all seven HMs and increased their concentrations in drainage water. Lower concentrations of Cd, Cu, Fe, Ni, and Zn in leachate from columns with EDTA and plants compared to columns with EDTA and no plants showed that poplars can reduce groundwater contamination by intercepting these HMs in the soil. But the poplar plants did not reduce Pb and Mn in the leachate from columns with EDTA. Concentrations of Cd and Pb in the leachate mobilized by EDTA remained above drinking‐water standards with or without plants. The results showed that a chelate (EDTA) should not be added to a soil at a sludge farm to enhance phytoremediation. The chelate mobilized HMs that leached to drainage water and contaminated it.     

Growth,survival, and heavy metal (Cd and Ni) uptake of spinach (Spinacia oleracea) and fenugreek (Trigonella corniculata) in a biochar‐amended sewage‐irrigated contaminated soil

Irrigation of arable land with contaminated sewage waters leads to the accumulation of trace metals in soils with subsequent phyto‐/zootoxic consequences. In this study, biochar derived from cotton sticks was used to amend an agricultural silt‐loam soil that had been previously irrigated with trace metal contaminated sewage waters. Metal accumulation and toxicity to spinach (Spinacia oleracea) and fenugreek (Trigonella corniculata) was investigated by measuring concentrations of Cd and Ni in plant tissues and various photosynthetic and biochemical activities of plants. Positive impacts of biochar on both spinach and fenugreek were observed in terms of biomass production that increased from 29% to 36% in case of spinach, while for fenugreek this increase was 32% to 36%. In the control treatment there was an increase in malondialdihyde, soluble sugar, and ascorbic acid contents, indicating heavy metal stress. Biochar applications increased soluble proteins and amino acids in plants and reduced the uptake of Cd from 5.42 mg kg^?1 at control to 3.45 mg kg^?1 at 5% biochar amended soil and Ni (13.8 mg kg^?1 to 7.3 mg kg^?1 at 5% biochar) by the spinach plants. In fenugreek, the Cd was reduced from 7.72 mg kg^?1 to 3.88 mg kg^?1 and reduction in Ni was from 15.45 mg kg^?1 to 9.46 mg kg^?1 at 5% biochar treated soil, reducing the possibility of transfer up the food chain. This study demonstrates that the use of biochar made from cotton‐sticks, as an amendment to arable soils that have received contaminated irrigation water, could improve plant growth and decrease Cd and Ni uptake to crops, alleviating some of the negative impacts of using sewage waters on arable land.     

Total soil heavy‐metal concentrations and mobile fractions after 10 years of biowaste‐compost fertilization

The accumulation of heavy metals (HMs) in soils is the most often cited potential risk of compost application. As the ecological effects of metals are related to mobile fractions rather than to total concentrations in the soil, we measured the total (aqua regia–extractable) HM concentrations, the readily available water‐soluble and the potentially bioavailable LiCl‐extractable fraction of soil HMs in a field experiment after 10 y with total applications of 95, 175, and 255 t ha^–1 biowaste compost (fresh matter). Total soil concentrations of Cd, Cr, Cu, Ni, and Pb in the compost treatments were not significantly higher than in the unfertilized control. Total Zn concentrations increased in the treatment with the highest application rate, as expected from the calculation of the Zn load in the composts. In the mobile fractions, as measured in soil saturation extract and LiCl extract, Cd and Pb were not detectable. Concentrations of Cr, Ni, and Zn were in the range published for unpolluted soils in other studies and did not show any differences according to treatment. Easily exchangeable Cu (in LiCl extract) was increased with compost fertilization, most probably due to complexation with low‐molecular organic complexants. Except for Cd and Zn, the results of the mobile HM fractions in the soil were in good agreement with plant HM concentrations. In conclusion, fertilization with high‐quality biowaste compost at such rates and after 10 y of application gives no cause for concern with regard to both total HM concentrations and available HM fractions.     

Growth and metal uptake of edamame [Glycine max (L.) Merr.] on soil amended with biosolids and gypsum

ABSTRACT

Although biosolids are a rich source of plant nutrients, there is concern about the potential heavy metal uptake by crops grown on biosolid-amended soils. This study was conducted to determine the effects of limed or composted biosolids and flue gas desulfurization gypsum (FGDG) on edamame growth, nodule development, and metal uptake. Two consecutive crops of edamame were grown on 40 and 80 T ha^?1 biosolid-amended soil with and without 10 T ha^?1 FGDG. Biosolids with or without FGDG did not reduce biomass, nodules, or grain yields in the first harvest and increased yields of all three tissues in the second harvest. Lead and cadmium concentrations in grain and biomass were below the instrument detection limits. Copper, manganese, and zinc were within the ranges normally found in soybean grain. In this pot study, biosolids and FGDG did not reduce edamame growth or increase grain metal concentrations to levels of concern.     

Biochar effects on soil chemical properties and mobilization of cadmium (Cd) and lead (Pb) in paddy soil

This study focused on the effects of biochar (BC) application on soil chemical properties and mobilization of cadmium (Cd) and lead (Pb) in the paddy soil. BC was applied at the rate of 0, 10, 20 and 40 t ha⁻¹, respectively. BC application caused a significant increase in soil organic carbon contents (SOC), pH, nitrate–nitrogen (-N),and available phosphorus contents (AP) in the top and subsurface soil, while SOC contents in the subsurface soil decreased with increasing rate of BC. BC40 effectively reduced the mobility of Cd and Pb from the top layer to the subsurface soil, while concentrations of Cd and Pb in the topsoil remained unchanged. Path analysis showed that the direct path coefficient AP was highest; SOC, -N and AP had a negative direct effect on the Cd and Pb in subsurface soil. Soil pH and -N had a high negative indirect effect through AP. The decision coefficient decreased in the following order: pH, AP, SOC, -N and -N. Regression analysis showed that soil Cd and Pb had a significant linear correlation with soil AP, whereas soil Pb also had a significant linear correlation with soil pH. In conclusion, BC40 can alter soil chemical properties and reduce the mobility of Cd and Pb from the top layer to the lower subsurface of the paddy soil.     

Mudflat soil amendment by sewage sludge: Soil physicochemical properties,perennial ryegrass growth,and metal uptake

Abstract

The fast pace of cropland loss in China is causing alarm over food security and China’s ability to remain self-reliant in crop production. Mudflats after organic amendment can be an important alternative cropland in China. Land application of sewage sludge has become a popular organic amendment to croplands in many countries. Nevertheless, the land application of sludge to mudflats has received little attention. Therefore, the objective of the present work was to investigate the impact of sewage sludge amendment (SSA) at 0, 30, 75, 150 and 300 t ha^?1 rates on soil physicochemical properties, perennial ryegrass (Lolium perenne L.) growth and heavy metal accumulation in mudflat soil. The results showed that the application of sewage sludge increased organic matter (OM) content by 3.5-fold while reducing salinity by 76.3% at the 300 t ha^?1 rate as compared to unamended soil. The SSA reduced pH, electric conductivity (EC) and bulk density in mudflat soil, increased porosity, cation exchange capacity (CEC) and contents of nitrogen (N), phosphorus (P), exchangeable potassium ions (K⁺), sodium ions (Na⁺), calcium ions (Ca²⁺) and magnesium ions (Mg²⁺) in comparison to unamended soil. There were 98.0, 146.6, 291.4 and 429.2% increases in fresh weight and 92.5, 132.4, 258.6 and 418.9% increases in dry weight of perennial ryegrass at 30, 75, 150, and 300 t ha^?1, respectively, relative to unamended soil. The SSA increased metal concentrations of aboveground and root parts of perennial ryegrass (p < 0.05). The metal concentrations in perennial ryegrass were Zn > Cr > Mn > Cu > Cd > Ni, and the metal concentrations in roots were significantly higher than aboveground parts. The metal accumulation in perennial ryegrass correlated positively with sludge application rates and available metal concentrations in mudflat soil. Land application of sewage sludge was proved to be an effective soil amendment that improved soil fertility and promoted perennial ryegrass growth in mudflat soil. However, heavy metal accumulation in plants may cause food safety concern.     

Field-Scale Assessment of Phytotreatment of Soil Contaminated with Weathered Hydrocarbons and Heavy Metals (9 pp)

Background, Aim and Scope   Phytoremediation is a remediation method which uses plants to remove, contain or detoxify environmental contaminants. Phytoremediation has successfully been applied for the removal of fresh hydrocarbon contamination, but removal of aged hydrocarbons has proven more difficult. Biodegradation of hydrocarbons in the subsurface can be enhanced by the presence of plant roots, i.e. the rhizosphere effect. Phytostabilization reduces heavy metal availability via immobilization in the rhizosphere. Soils contaminated by both hydrocarbons and heavy metals are abundant and may be difficult to treat. Heavy metal toxicity can inhibit the activity of hydrocarbon-degrading microorganisms and decrease the metabolic diversity of soil bacteria. In this experiment, weathered hydrocarbon- and heavy metal- contaminated soil was treated using phytoremediation in a 39- month field study in attempts to achieve both hydrocarbon removal and heavy metal stabilization. Materials and Methods: A combination of hydrocarbon degradation and heavy metal stabilization was evaluated in a field-scale phytoremediation study of weathered contaminants. Soil had been contaminated over several years with hydrocarbons (11400±4300 mg kg dry soil)-1 and heavy metals from bus maintenance activities and was geologically characterized as till. Concentrations of soil copper, lead and zinc were 170±50 mgkg-1, 1100±1500 mg kg-1 and 390±340 mg kg-1, respectively. The effect of contaminants, plant species and soil amendment (NPK fertilizer or biowaste compost) on metabolic activity of soil microbiota was determined. Phytostabilization performance was investigated by analyses of metal concentrations in plants, soil and site leachate as well as acute toxicity to Vibrio fischeri and Enchtraeus albidus. Results: Over 39 months hydrocarbon concentrations did not decrease significantly (P=0.05) in non-amended soil, although 30% of initial hydrocarbon concentrations were removed by the last four months of study. In soil amended with NPK fertilizer and municipal biowaste compost, 65 % and 60 % of hydrocarbons were removed, respectively. The soil contained metabolically diverse bacteria, measured as carbon source utilization and extracellular enzymatic activities. Compost addition resulted in a slight increase in enzymatic activities. Diesel fuel utilization potential in Biolog MT2 plates inoculated with a soil suspension was enhanced by both compost and NPK compared to non-amended soil. Soil toxicity to V. fischeri and E. albidus was low. The leachate was not toxic to V. fischeri. Pine (Pinus sylvestris), poplar (Populus deltoides x Wettsteinii), grasses and clover (Trifolium repens) survived to varying degrees in the contaminated soil. All plants suffered from phytotoxicity symptoms and some trees died during the study period. Plants formed a dense cover over the compost-amended soil, whereas non-amended soil had areas devoid of vegetation throughout the study. Vegetation coverage in the NPK-amended quarter was about 50 % after the first four months of study, but increased gradually to 100 %. Heavy metals did not accumulate in plant tissue. Discussion: Removal of hydrocarbons from weathered unfertilized hydrocarbon-contaminated soil was not statistically significant despite the presence of a viable hydrocarbon-degrading microbial community. This effect is attributed to soil heterogeneity and low bioavailability of hydrocarbons. Hydrocarbon concentrations were not reduced to the desired level, i.e., 1500 mg hydrocarbons (kg of dry soil)-1, in any treatment. . The presence of clay minerals and organic matter within the compost may have limited heavy metal transfer to leachate and plant tissue. Conclusions: Weathered hydrocarbons were partly decomposed in soil fertilized with NPK fertilizer or biowaste compost, but not from unfertilized soil. The active hydrocarbon-degrading microbiota and low toxicity of soil to V. fischeri and E. albidus indicates low availability of contaminants to microorganisms. Despite high heavy metal concentrations, the soil contained metabolically diverse bacteria, measured as carbon source utilization and extracellular enzymatic activities. Heavy metals did not accumulate in test plants. Pine and poplar suffered from phytotoxicity symptoms in the soil and could not enhance hydrocarbon removal in compost-amended soil. Compost addition combined with a grass and legume crop is suggested for stabilization of combined hydrocarbon- and metal-contaminated soil. Recommendations and Perspectives: Both compost and NPK fertilizers can be used to enhance phytoremediation of soil contaminated with weathered hydrocarbons in the presence of heavy metals; however, compost addition is recommended since it enables greater vegetative coverage. This in turn may decrease heavy metal mobility. Phytoremediation can be used for remediation of soil contaminated with weathered hydrocarbons in the presence of heavy metals. However, phytoremediation of weathered contaminants requires extended periods of time; thus, other remediation methods should be considered in the event of soil contamination posing an immediate public health and/or environmental threat.     

Bestimmung von Mikronährstoffen und Schwermetallen in Böden mit dem Verfahren der Elektro‐Ultrafiltration (EUF) durch Zugabe von DTPA

With the electro–ultrafiltration (EUF) technique, the plant availability of several plant nutrients in soils can be characterized. The basic principle of EUF is that an electric field is induced using platinum electrodes. Ions in the soil suspension move either to the cathode or to the anode and are filtrated through ultra‐membrane filters. In the standard EUF procedure, two extractions steps are used: 30 min at 20°C and 5 min at 80°C. However, the determination of micronutrients and heavy metals with the standard EUF procedure is not possible, because the solubility of these elements in water is low and most of the watersoluble elements are precipitated when passing the platinum electrodes. The addition of DTPA, a well known complexing agent, during a third EUF fraction (5 min at 80°C) enables extraction of micronutrients and heavy metals. Highest concentrations in the 33 soils of the study were found for iron, followed by zinc, manganese, lead, copper, and nickel. Lower concentrations were obtained for cobalt, chromium, cadmium, and molybdenum. For two soils, the EUF/DTPA procedure was compared to CaCl₂/DTPA and EDTA soil extraction methods, showing that higher or comparable amounts were found with CaCl₂/DTPA and much higher amounts with the EDTA method. These results reveal that the EUF/DTPA technique in principle can be used for the determination of plant‐available micronutrients and heavy metals. However, in a next step the relationship between EUF/DTPA‐extractable elements and their availability for plants needs to be quantified.     

Plant availability and leaching of (heavy) metals from ammonium‐, calcium‐, carbohydrate‐, and citric acid‐treated uranium‐mine‐dump soil

Remediation of an uranium‐mine soil from Settendorf (East Germany) includes phytoextraction under conditions which make its heavy metals more plant‐available but less leachable. A second way is active inhibition of heavy metal uptake by the plant. In a pot trial with Chinese cabbage (Brassica chinensis L.), planted and unplanted soil samples were daily irrigated with deionized water or aqueous solutions with a total of (g (kg soil)^–1) CaCl₂ (0.26 Ca), NH₄Cl (1.39), casein, sucrose, citric acid (13), and an extract of rape (B. napus L.) shoots (13 DW) in a phytotron for 26 d. Water‐irrigated plants were also treated with a 50 mM citric acid solution (10.5 g (kg soil)^–1) 6 and 7 d prior to harvesting. Total elements in plant tissue and soluble elements in aqueous extracts from control and postharvest soils were determined by ICP‐AES. Supplements of NH , and the NH ‐generating casein and rape extract reduced soil pH during nitrification, and increased plant uptake of Cd, Cu, Ni, and Zn. Citric acid at 50 mM adjusted soil to pH 4.5–6.0 and enhanced uptake of all elements. Long‐term application of sucrose and citric acid increased pH and inhibited uptake of Cd, Cr, Cu, Ni, and Zn. Contemporarily, leaching of heavy metals and humic substances was lowest with Ca and NH and highest with sucrose and citric acid amendments. It is concluded that Chinese cabbage grown for chelate‐assisted phytoextraction should be supplied with Ca and NH to obtain a high plant biomass on soil with a low hazard of leaching. Metal uptake should be stimulated by application of chelator 7 d prior to harvesting. Undesired uptake of heavy metals by Chinese cabbage determined as food should be inhibited with carbohydrate amendments. Long‐term application of NH or chelator, which reduces the solubility of certain elements but increases their uptake moderately, is recommended as a tool for continuous phytoextraction technologies.     

Uptake and apoplastic retention of EDTA‐ and phytosiderophore‐chelated chromium(III) in maize

Increasing the mobilization and root uptake of chromium (Cr) by synthetic and plant‐borne chelators might be relevant for the design of phytoremediation strategies on Cr‐contaminated sites. Short‐term uptake studies in maize roots supplied with ⁵¹CrCl₃ or ⁵¹Cr(III)‐EDTA led to higher apoplastic Cr contents in plant roots supplied with ⁵¹CrCl₃ and in Fe‐sufficient plants relative to Fe‐deficient plants, indicating that Fe stimulated co‐precipitation of Cr. Concentration‐dependent retention of Cr in a methanol:chloroform‐treated cell‐wall fraction was still saturable and in agreement with the predicted tendency of Cr(III) to precipitate as Cr(OH)₃. To investigate a possible stimulation of Cr(III) uptake by phytosiderophores, Fe‐deficient maize roots were exposed for 6 d to Cr(III)‐EDTA or Cr(III)‐DMA (2'‐deoxymugineic acid). Relative to plants without Cr supply, the supply of both chelated Cr species in a subtoxic concentration of 1 µM resulted in alleviation of Fe deficiency–induced chlorosis and higher Cr accumulation. Long‐term Cr accumulation from Cr(III)‐DMA was similar to that from Cr(III)‐EDTA, and Cr uptake from both chelates was not altered in the maize mutant ys1, which is defective in metal‐phytosiderophore uptake. We therefore conclude that phytosiderophores increase Cr solubility similar to synthetic chelators like EDTA, but do not additionally contribute to Cr(III) uptake from Cr‐contaminated sites.     

利用作物生长模型和时序信号甄别水稻镉胁迫

在自然农田生态系统中,农作物的生长通常受到各类环境胁迫（如重金属胁迫、病虫害、水分、营养）的影响,如何区分重金属胁迫与其他胁迫有待进一步研究。该研究选取了湖南省株洲为试验区,收集2017-2019年的Sentinel-2卫星影像数据,结合野外实测数据,开展水稻重金属镉（Cd）胁迫识别研究。首先,利用作物生长模型World Food Studies（WOFOST）同化时序遥感数据获取每年的叶面积指数（Leaf Area Index,LAI）时间序列曲线;然后运用集合经验模态分解（Ensemble Empirical Mode Decomposition,EEMD）方法对LAI时间序列进行多尺度分解,得到不同的时序信号分量（Intrinsic Mode Function,IMF）;最后使用动态时间规整（Dynamic Time Warping,DTW）方法计算受胁迫水稻分解后的时间序列与健康水稻分解后的时间序列之间的DTW距离,即归一化胁迫指数。结果表明：归一化胁迫指数是水稻重金属胁迫敏感的参数,与土壤重金属含量的相关系数为0.851,水稻受到的胁迫程度越高,归一化胁迫指数值越大,反之越低;在试验区中,水稻重度重金属胁迫的分布面积比例相对较低,且主要集中在西部、东北部以及偏东南地区。融合集合经验模态分解和动态时间规整方法能有效地甄别并定量分析水稻重金属胁迫状况,从而为作物重金属污染胁迫监测提供重要参考。     

Spatial distribution of soil heavy metal concentrations as indicator of pollution sources at Mount Križna (Great Fatra,central Slovakia)

The objective of this study was to test the suitability of a simple approach to identify the direction from where airborne heavy metals reach the study area as indication of their sources. We examined the distribution of heavy metals in soil profiles and along differently exposed transects. Samples were taken from 10 soils derived from the same parent material along N-, S-, and SE-exposed transects at 0—10, 10—20, and 20—40 cm depth and analyzed for total Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn concentrations. The heavy metal concentrations at 0—10 cm were larger than background concentrations in German arable soils except for Cr (Cd: 0.6—1.8 mg kg^—1; Cr: 39—67; Cu: 40—77; Ni: 87—156; Pb: 48—94; Zn: 71—129; Fe: 26—34 g kg^—1; Mn: 1.1—2.4). Decreasing Cd, Cu, Mn, and Pb concentrations with increasing soil depth pointed at atmospheric inputs. Aluminum and Ni concentrations increased with soil depth. Those of Fe, Cr, and Zn did not change with depth indicating that inputs at most equalled leaching losses. The Pb accumulation in the surface layer (i.e. the ratio between the Pb concentrations at 0—10 to those at 20—40 cm depth) was most pronounced at N-exposed sites; Pb obviously reached Mount Križna mainly by long-range transport from N where several industrial agglomerations are located. Substantial Cd, Cu, and Mn accumulations at the S- and SE-exposed sites indicated local sources such as mining near to the study area which probably are also the reason for slight Cr and Zn accumulations in the SE-exposed soils. Based on a principal component analysis of the total concentrations in the topsoils four metal groups may be distinguished: 1. Cr, Ni, Zn; 2. Mn, Cd; 3. Pb (positive loading), Cu (negative loading); 4. Al, Fe, indicating common sources and distribution patterns. The results demonstrate that the spatial distribution of soil heavy metal concentrations can be used as indication of the location of pollution sources.     

Kinetics of zinc uptake by mycorrhizal (VAM) and non-mycorrhizal corn (Zea mays L.) roots

Summary The kinetics of Zn absorption were studied in mycorrhizal (Glomus macrocarpum) and non-mycorrhizal roots of corn (Zea mays L.) at pH 6.0 at Zn concentrations of 75 mol to 1.07 mol m^-3. Five concentration-dependent phases of Zn absorption were recognized; phase 0 (1.5–4.0 mmol m^-3) was linear but the other four phases (4.0 mmol to 1.07 mol m^-3) obeyed Michaelis-Menten kinetics. At low concentrations (less than 4 mmol m^-3), sigmoidal kinetics of Zn absorption were observed. The absorption of Zn by mycorrhizal maize was greater at low concentrations but decreased at higher levels. This appeared to be a result of a higher maximal uptake rate in phase 1 and lower K _m values in the subsequent phases. Kinetic models yielding continuous isotherms could not account for the observed multiphasic pattern.Research paper no. 6820 through the Director, Experiment Station, G.B. Pant University of Agriculture and Technology, Pantnagar 263 145, UP, India     

Effects of Crystal Modification on the Binding of Trace Metals and Arsenate by Goethite (7 pp)

-  Dedicated to Prof. Dr. Ulrich Förstner on his 65th birthdayGoal, Scope and Background   Goethite (&#945;-FeOOH) as the most frequently occurring iron oxide in the environment plays a significant role in the binding of inorganic pollutants. Accordingly, synthetic goethite is used for the purification of contaminated water. Goethite crystals can be prepared in different shape as porous and non-porous forms. The mineral can also be modified by partial substitution of structural Fe+3 for different foreign elements. The biggest possible substituent known so far is Cd+2 which causes a strong expansion of the unit-cell parameters. An incorporation of Pb+4 generates a permanent positive charge. Goethites with these morphological and structural modifications were selected for sorption experiments with Co2+, Ni2+, Zn2+, Cd2+, Pb2+, and arsenate. It was intended to demonstrate the potential of mineral modification for improving sorption properties.Methods   Batch sorption studies were carried out combining each mineral with a single element at different pH and reaction times. Cations were investigated at a single initial concentration only while arsenate was tested over a range of concentrations in order to establish sorption isotherms. The sorption step was followed by an extraction step to characterize time dependent immobilization reactions.Results and Discussion   A time dependent increase of trace metal and arsenate sorption is attributed to a migration of ions into pores of star-shaped goethite and to a binding by specific sorption sites at the surface. The migration into pores is related to the size of adsorbing cations. The almost identical sorption behaviour of Ni2+ and Co2+ on pure goethite is contrasted by a strong preference of Co over Ni on Cd-goethite. Expansion of the unit-cell dimensions in Cd+2 substituted goethite generates highly specific binding sites at the surface. These are accessible to Co and Zn only. A permanent positive charge in Pb+4 substituted goethite reduces the binding of cations and doubles the sorption capacity for arsenate. Pb-goethite also contains a limited portion of highly specific sites which can only be accessed by Zn2+. Immobilization takes place even after a short contact time of 16 hours. This process results in a growing fraction of non-extractable metals and arsenate with reaction time.Conclusions   Pores and foreign elements in the goethite structure greatly affect the reactivity of the mineral and the ability to immobilize inorganic pollutants. A possible mechanisms for the preferred sorption of Co and Zn by Cd-goethite is seen in the ability of these metal ions to adopt a smaller size: Co by oxidation of Co2+ to Co3+ and Zn by tetrahedral coordination of Zn2+. This kind of binding can be viewed as structural incorporation. The binding properties of modified goethites can well be characterized by sorption tests including an array of elements with different ionic size and charge.Recommendation and Outlook   There is considerable potential for designing goethite modifications with improved surface reactivity for specific purposes such as water purification and possibly catalysis of reactions.     

Localized application of sewage sludge improved plant nitrogen and phosphorus uptake by rhizobox‐grown spring wheat

Sewage sludge (SS) can be used as an alternative fertilizer in agriculture. It is normally broadcasted and plowed into soil, but it is not clear if it has a potential as a placement fertilizer. A rhizobox experiment was conducted to investigate the placement effect of SS and mineral nitrogen (N) fertilizer on shoot and root growth as well as nutrient uptake of spring wheat (Triticum aestivum L.). The treatments included localized SS, mixed SS, localized SS and ammonium, localized ammonium, and a control without addition of SS and ammonium to examine the effect of SS placement and, further, if ammonium co‐localization would enhance the placement effect. The results show that SS fertilization improved soil N and P availability, which significantly increased plant N and P uptake and enhanced shoot growth, while root length was significantly reduced compared to the control. Localized SS increased root proliferation in the placement region, resulting in enhanced uptake of P from the SS patch compared to homogenous application. However, co‐localized application of ammonium with SS significantly depressed plant shoot and root growth. Localized ammonium markedly restricted root proliferation in the placement region and reduced soil pH in both bulk soil and placement region, contributing to decreased nutrient uptake and plant growth.     

Cadmium‐ and barium‐toxicity effects on growth and antioxidant capacity of soybean (Glycine max L.) plants,grown in two soil types with different physicochemical properties

The pollution of agricultural soils by metals is of growing concern worldwide, and is increasingly subject to regulatory limits. However, the effect of metal pollutants on the responses of plants can vary with soil types. In this study, we examined the growth and antioxidant responses of soybean plants exposed to contrasting soils (Oxisol and Entisol), which were artificially contaminated with cadmium (Cd) or barium (Ba). Cadmium reduced plant growth at concentrations higher than 5.2 mg (kg soil)^–1, while Ba only affected plant growth at 600 mg kg^–1. Such levels are higher than the limits imposed by the Brazilian environmental legislation. Lipid peroxidation was increased only at a Cd concentration of 10.4 mg kg^–1 in the Oxisol, after 30 d of exposure. Twelve superoxide dismutase (SOD; EC 1.15.1.1) isoenzymes were evaluated, most of which were classified as Cu/Zn forms. The SOD activity in the leaves of plants grown in the Oxisol decreased over time, whilst remaining high in the Entisol. Catalase (CAT; EC 1.11.1.6) activity in the leaves exhibited little response to Cd or Ba, but increased over time. Glutathione reductase (GR; EC 1.6.4.2) activity was reduced over time when exposed to the higher Cd concentrations, but increased following Ba exposure in the Oxisol. The enzyme‐activity changes were mainly dependent on soil type, time of exposure and, to a lesser extent, the metal concentration of the soil. Soybean plants grown in a sandy soil with a low buffering capacity, such as Entisol, suffer greater oxidative stress than those grown in a clay soil, such as Oxisol.     

香蕉皮改性材料对废水中二价Cd离子的吸附特性与机理

为探究农业生物质制备绿色吸附材料处理含Cd~(2+)废水方法,以香蕉皮为原料,制备改性吸附材料。采用单因素试验,优化了改性工艺条件。通过静态吸附试验,结合等温模型和吸附动力学模型探讨了其对Cd~(2+)吸附过程。利用比表面及孔径分析(brunner-emmet-teller)、扫描电镜(scanning electron microscope)、能谱仪(energy disperse spectroscopy)、元素分析仪、傅里叶变换红外光谱(Fourier transform infrared spectroscopy)等手段对改性前后材料的表面形态和结构进行表征,并分析了改性和吸附过程的机理。结果表明:改性较佳工艺条件为Na OH浓度为0.25 mol/L,改性时间为30 min。在此条件下香蕉皮改性后,对水中Cd~(2+)的理论饱和吸附量由37.61 mg/g提高到87.15 mg/g,平衡时间由60 min缩短到45 min。吸附符合Langmuir等温模型(R~2=0.998)和准二级动力学模型(R2=0.999)。改性后的香蕉皮对水中Cd~(2+)的吸附以离子交换吸附为主。研究结果可为木质纤维素生物质改性制备绿色吸附材料处理含重金属废水提供理论依据。     

Enhancement of arbuscular mycorrhizal fungus (Glomus versiforme) on the growth and Cd uptake by Cd-hyperaccumulator Solanum nigrum

Arbuscular mycorrhizal fungus (AMF) can enhance plant growth and resistance to toxicity produced by heavy metals (HMs), affect the bioavailability of HMs in soil and the uptake of HMs by plants, and thus has been emerged as the most prominent symbiotic fungus for contribution to phytoremediation. A greenhouse pot experiment was conducted to assess the effect of Glomus versiforme BGC GD01C (Gv) on the growth and Cd accumulation of Cd-hyperaccumulator Solanum nigrum in different Cd-added soils (0, 25, 50, 100 mg Cd kg⁻¹ soil). Mycorrhizal colonization rates were generally high (from 71% to 82%) in Gv-inoculated treatments at all Cd levels. Gv colonization enhanced soil acid phosphatase activity, and hence elevated P acquisition and growth of S. nigrum at all Cd levels. Moreover, the presence of Gv significantly increased DTPA-extractable (phytoavailable) Cd concentrations in 25 and 50 mg Cd kg⁻¹ soils, but did not affect phytoavailable Cd in 100 mg Cd kg⁻¹ soil. Similarly, inoculation with Gv significantly increased Cd concentrations of S. nigrum in 25 and 50 mg Cd kg⁻¹ soils, but decreased Cd concentrations of the plants in 100 mg Cd kg⁻¹ soil. Overall, inoculation with Gv greatly improved the total Cd uptakes in all plant tissues at all Cd levels. The present results indicated that S. nigrum associated with Gv effectively improved the Cd uptake by plant and would be a new strategy in microbe-assisted phytoremediation for Cd-contaminated soils.     

The Characterization of Heavy Metals in the Grapevine (Vitis vinifera) Cultivar Rkatsiteli and Wild Blackberry (Rubus fruticosus) from East Serbia by ICP-OES and BAFs

Inductively coupled plasma optical emission spectroscopy, in combination with calculation of various biological factors, was used in this study not only for a simple illustration of the present status of some essential and non-essential metals such as copper (Cu), zinc (Zn), nickel (Ni), lead (Pb), arsenic (As), and cadmium (Cd) in the grapevine cultivar Rkatsiteli and wild blackberry from East Serbia but also for the estimation of plant bioaccumulation potentials. Great majority of detected metal concentrations were in normal ranges except in few cases: Zn concentrations were at the level of deficiency in almost all plant parts, and some Cu and As concentrations were at the levels that could be considered phytotoxic. Biological accumulation factors provided very informative data on metal accumulation and translocation in both plants and pointed to low accumulation rates of metals except in the case of Cu, Zn, and As in some wild blackberry tissues.