Effect of o-phenylenediamine on Cu adsorption and desorption in red soil and its uptake by paddy rice (Oryza sativa)

A study was carried out of Cu adsorption and desorption processes in red soil as affected by o-phenylenediamine (o-PD) in the range 0-80 mg/l. The results indicated that the presence of o-PD enhanced Cu adsorption in red soil in weakly acid media, meanwhile, desorption percentage of Cu from soil, extracted by 1.0 M MgCl(2), also increased when Cu adsorption in soil occurred in the presence of o-PD. The response of paddy rice to Cu in red soil shows that Cu toxicity was mitigated in the presence of o-PD and that the Cu concentration in rice straw decreased with increasing concentration of o-PD from 0 to 4.0 mmol/kg in soil. The fractions of background Cu in soil did not change noticeably in the presence of o-PD, whereas the effect of o-PD on the fractions of added Cu was significant. It was found that the exchangeable and carbonate bound Cu fractions decreased and the fraction of Cu bound to Fe-Mn oxides and organic matter increased with increasing o-PD concentration in soil when Cu was added at the same rate. Copper concentration in rice straw was significantly correlated with exchangeable Cu (r=0.961) and carbonate bound Cu (r=0.959) in soil. This result implicates that the behavior of Cu in soil is likely to be affected by organic pollutants containing amino groups.     

Fractionation and bioavailability of metals and their impacts on microbial properties in sewage irrigated soil

A study was conducted to evaluate the effect of long-term irrigation of sewage contaminated with heavy metals like Cd, Cr, Cu and Pb on microbial and biochemical parameters of soils of West Bengal, India. The microbial parameters included microbial biomass carbon (MBC), microbial metabolic quotient; the biochemical parameters included fluorescein diacetate hydrolyzing activity, beta-glucosidase, urease, phosphatase, and aryl sulphatase activities. A sequential extraction technique was used to quantify water soluble, exchangeable, carbonate bound, Fe/Mn-oxide bound, organically bound, and residual metal fractions. Metal concentrations in the two most labile fractions (i.e., water soluble and exchangeable fractions) were generally low. Total metal concentrations at each site seemed to be associated with soil amorphous Fe and Al minerals. The MBC and the enzymes studied were significantly and negatively correlated with water soluble and exchangeable metals but not significantly correlated with other forms, indicating that water soluble and exchangeable forms exerted a strong inhibitory effect on the soil microbial and biochemical parameters. It was concluded that irrigating soils with metal contaminated sewage seemed to damage soil quality in the long term.     

Accumulation and fractionation of copper, iron, manganese, and zinc in calcareous soils amended with composts.

Amending soils with compost may lead to accumulation of metals and their fractions at various concentrations in the soil profile. The objectives of this study were to determine 1) the accumulation of Cu, Fe, Mn, and Zn with depth and 2) the distribution of water soluble, exchangeable, carbonate, Fe-Mn oxides, organic and residual forms of each metal in soils amended with MSW compost, co-compost, biosolids compost and inorganic fertilizer (as control). Total concentrations of Cu, Fe, Mn and Zn were concentrated in the 0-22 cm soil layer and scant in the rock layer. These metals were in the decreasing order of Fe > Mn > Zn > or = Cu. Copper, Fe, and Zn were predominantly in the residual form followed by fractions associated with Fe-Mn oxides, carbonate, organic, exchangeable and water soluble in all treatments except MSW compost amended soil where the organic fraction was higher than the carbonate fraction. In fertilizer, co-compost and biosolids compost treated soils Mn concentrated mainly in the Fe-Mn oxides form followed by residual, carbonate, and organic forms whereas, in MSW compost treated soil the same pattern occurred except that Mn organic fraction was higher than that in the carbonate form. The MSW compost has a greater potential to be used as a soil amendment to supply plants with Cu, Mn and Zn than other treatments in calcareous soils of south Florida.     

Speciation of chromium in 12 agricultural soils from Turkey

The objective of the study was to speciate and to evaluate various soil Cr species in relation to soil properties. Surface soil samples were taken from outskirts of the Cr factory and applied a sequential extraction procedure. Extracts analyzed in atomic absorption spectrophotometry (AAS). Chromium was partitioned into exchangeable Cr, Cr bound to carbonate, Fe-Mn oxide, and organic matter, and residual Cr. The most common form of chromium was in the residual form, followed by the organic form. Very low concentrations of Cr were found in the exchangeable and carbonate forms. Mean values of the extractable forms of Cr, expressed in percentages of total soil contents were: 0.94% exchangeable, 0.80% carbonates, 2.13% oxides, 7.08% organics and 89.81% residual. Multiple regression analysis of analytical data revealed that soil pH, contents of organic matter and calcium carbonate were the most important factor controlling the distribution of Cr forms determined.     

Distribution and variability of redox zones controlling spatial variability of arsenic in the Mississippi River Valley alluvial aquifer, southeastern Arkansas

Twenty one of 118 irrigation water wells in the shallow (25-30 m thick) Mississippi River Valley alluvial aquifer in the Bayou Bartholomew watershed, southeastern Arkansas had arsenic (As) concentrations (<0.5 to 77 microg/L) exceeding 10 microg/L. Sediment and groundwater samples were collected and analyzed from the sites of the highest, median, and lowest concentrations of As in groundwater in the alluvial aquifers located at Jefferson County, Arkansas. A traditional five-step sequential extraction was performed to differentiate the exchangeable, carbonate, amorphous Fe and Mn oxide, organic, and hot HNO(3)-leachable fraction of As and other compounds in sediments. The Chao reagent (0.25 M hydroxylamine hydrochloride in 0.25 M HCl) removes amorphous Fe and Mn oxides and oxyhydroxides (present as coatings on grains and amorphous minerals) by reductive dissolution and is a measure of reducible Fe and Mn in sediments. The hot HNO(3) extraction removes mostly crystalline metal oxides and all other labile forms of As. Significant total As (20%) is complexed with amorphous Fe and Mn oxides in sediments. Arsenic abundance is not significant in carbonates or organic matter. Significant (40-70 microg/kg) exchangeable As is only present at shallow depth (0-1 m below ground surface). Arsenic is positively correlated to Fe extracted by Chao reagent (r=0.83) and hot HNO(3) (r=0.85). Arsenic extracted by Chao reagent decreases significantly with depth as compared to As extracted by hot HNO(3). Fe (II)/Fe (the ratio of Fe concentration in the extracts of Chao reagent and hot HNO(3)) is positively correlated (r=0.76) to As extracted from Chao reagent. Although Fe (II)/Fe increases with depth, the relative abundance of reducible Fe decreases noticeably with depth. The amount of reducible Fe, as well as As complexed to amorphous Fe and Mn oxides and oxyhydroxides decreases with depth. Possible explanations for the decrease in reducible Fe and its complexed As with depth include historic flushing of As and Fe from hydrous ferric oxides (HFO) by microbially-mediated reductive dissolution and aging of HFO to crystalline phases. Hydrogeochemical data suggests that the groundwater in the area falls in the mildly reducing (suboxic) to relatively highly reducing (anoxic) zone, and points to reductive dissolution of HFO as the dominant As release mechanism. Spatial variability of gypsum solubility and simultaneous SO(4)(2-) reduction with co-precipitation of As and sulfide is an important limiting process controlling the concentration of As in groundwater in the area.     

Phytotoxic lesions of chromium in maize

Chromium (Cr) is fairly abundant in the earth's crust and ranks fourth among the 29 elements of biological importance. Besides natural sources, Cr enters biotic components of the ecosystem in various ways. Of other major industrial sources, tanning and chrome-plating industries are prominent sources. Cr(VI) form of chromium is highly reactive and influences both plants and animals. Due to Mn present in soil, Cr(III) is oxidized to Cr(VI) which remains in soil for a long time and can affect plant growth and development. Since maize is an important food and fodder plant for human beings and cattle, a study was conducted to investigate the effects of Cr on some metabolic activities of maize (Zea mays L. cv. Ganga 5). Chromium caused visible lesions of interveinal chlorosis. Young leaves showed vein clearing. Also, a papery appearance was observed in leaves. Margins of leaves were curled and the leaves appeared pale at greater Cr exposure. Concentrations of both chlorophyll a and b were reduced by exposure to Cr, the activities of ribonuclease and phenyl phosphatase were greater while the activity of iron-porphyrin enzyme catalase was less and the activity of amylase was also much less in plants exposed to Cr. Chromium also caused retardation of soluble protein. Accumulation of Cr in roots was much at all the levels of chromium supply. Exposure to Cr resulted in reduction in grain production and quality.     

Occurrence of arsenic in brown rice and its relationship to soil properties from Hainan Island, China

The acquaintance of arsenic concentrations in rice grain is vital in risk assessment. In this study, we determined the concentration of arsenic in 282 brown rice grains sampled from Hainan Island, China, and discussed its possible relationships to the considered soil properties. Arsenic concentrations in the rice grain from Hainan Island varied from 5 to 309 μg/kg, with a mean (92 μg/kg) lower than most published data from other countries/regions and the maximum contaminant level (MCL) for As_i in rice. The result of correlation analysis between grain and soil properties showed that grain As concentrations correlated significantly to soil arsenic speciation, organic matter and soil P contents and could be best predicted by humic acid bound and Fe-Mn oxides bound As fractions. Grain arsenic rises steeply at soil As concentrations lower than 3.6 mg/kg and gently at higher concentrations.     

Municipal waste compost as an alternative to cattle manure for supplying potassium to lowland rice

The importance of the use of potassium in agriculture is increasing in South Asia for making most productive use of the nutrient in terms of economic returns. Nutrient supply traditionally by cattle manure is constrained by its insufficient availability. Municipal waste compost may be an alternative source of nutrient supplements. Field experiments were conducted at the Experimental Farm of Calcutta University, West Bengal, India during the wet seasons of 1997, 1998 and 1999 on flooded lowland rice. Potassium fractions in municipal waste compost and cattle manure were determined by sequential extraction and also the potassium uptake by rice to compare the effectiveness of municipal waste compost with traditional manure. Potassium was significantly bound to the organic matter in municipal waste compost. Potassium uptake by rice grain and straw increased significantly with the combined application of organics and fertilizers and it was higher in grain than in straw. Water-soluble and non-exchangeable potassium contents of municipal waste compost and cattle manure were highly correlated with the uptake of potassium by straw and grain. Exchangeable and residual potassium were also significantly correlated with the uptake of potassium by straw and grain of rice. Much higher uptake of K in rice straw and rain resulted from applying the manures in conjunction with fertilizers than when applied singly.     

Distribution and Fractionation of Phosphorus,Cadmium, Nickel,and Lead in Calcareous Soils Amended with Composts

Abstract

Composts improve organic carbon content and nutrients of calcareous soils but the accumulation and distribution of phosphorus and heavy metals among various fractions in soil may vary under the south Florida conditions. The accumulation of P, Cd, Ni, and Pb with depth and the distribution of water soluble, exchangeable, carbonate, Fe–Mn oxides, organic and residual forms of each element were investigated in soils amended with municipal solid waste (MSW) compost, co-compost and biosolids compost and inorganic fertilizer (as control). Total concentrations of P, Cd, Ni, and Pb were higher in the 0–22 cm soil layers and decreased considerably in the rock layers. These elements were in the decreasing order of P ? Pb > Ni > Cd. Amounts of water soluble and exchangeable forms of P, Cd, Ni and Pb were negligible at 0–22 cm soil depths except for Cd in the 10–22 cm depth. Amending calcareous soil with either organic or inorganic amendments rendered phosphorus, nickle and lead in the residual form followed by Fe–Mn oxides form in the 0–10 and 10–22 cm soil layers. Cadmium was predominantly in the Fe–Mn oxides fraction followed by the residual and carbonate forms in both soil layers. A significant positive correlation was found between various organic carbon fractions and organic forms of P, Cd and Pb in the surface soil layer. Soil amended with MSW compost had higher concentration of Cd in the organic fraction whereas, co-compost and MSW compost amended soil had higher concentrations of organic Ni fraction in the 0–10 cm soil layer.     

Distribution, origin and fate of chromium in soils in Guanajuato, Mexico

Total, hexavalent and trivalent chromium were determined in surface and 30-cm depth soil samples from a highly chromium-polluted area in Guanajuato state, central México. Four samples were also analyzed by a sequential extraction procedure. Nearly 0.9 km(2) out of the 8 km(2) area sampled was polluted with chromium, at concentrations up to 12960 mg kg(-1), mostly as Cr(III). Concentrations of Cr(VI) were lower than 0.5 mg kg(-1) in most sampled points, with the exception of one, where the concentration was found to be 65.14 mg kg(-1). Chromiumcontaining dust from a chromate factory accounted for most of the contamination. The highest concentrations of hexavalent chromium in soil, were in the bottom sediments of an abandoned water reservoir used to store polluted water from a well, before use of the water in the factory process. Tannery wastes, dust from a sanitary landfill of chromate compounds and the transport of chromium products are the sources of chromium at other sites. Chromium is fixed preferentially in the hydrous Fe and Mn oxides in the more polluted soils. Less polluted soils have a high proportion of chromium associated with the sulfide and organic fraction. Cr(III) is retained preferentially in the superficial soil layer. Variations in the physical characteristics of the soil, relative abundance of the various soil components and characteristics of the contaminant source, give rise to differences in chromium soil concentrations with depth.     

Effects of development time, biomass and ferromanganese oxides on nickel sorption by stream periphyton

Procedurally defined periphyton frequently includes substantial quantities of hydrous iron (Fe) and manganese (Mn) oxides. As these oxides are strong sorbers of heavy metals, their presence may complicate estimation of metal bioaccumulation by periphyton. We examined the relationship between nickel (Ni) sorption and the development time, biomass, and Fe and Mn oxide content of stream periphyton. Development time, the time during which periphyton accrued on submerged tile substrata, was used to provide variation in biomass, Fe and Mn levels. Stream periphyton from four development times was exposed to Ni for 2 h in the laboratory, and then ashed. Development time was significantly associated with ash-free dry mass (AFDM), Fe and Mn levels (ANOVA, P < or = 0.003). Ni extracted by a mild reductant (hydroxylamine hydrochloride) was significantly associated with development time, and with AFDM, Fe and Mn levels (linear models, P < or = 0.0002). A subsequent acid digestion yielded similar associations with the same variables (linear models, P < or = 0.0001). For both extractions, AFDM was significantly and positively correlated with Fe (r = 0.68 and 0.89) and with Mn (r = 0.77 and 0.93) (Spearman rank, P < or = 0.005). These data demonstrate the importance of periphyton development time in influencing both metal sorption and levels of biomass and ferromanganese oxides. The data also suggest that metal contaminant levels in periphyton should not be attributed automatically to biotic sorption. Periphyton metal-accumulation studies conducted where ferromanganese oxide concentrations are elevated should address the potential metal-sorbing roles of Fe and Mn oxides within the periphyton matrix.     

The influence of pH and organic matter content in paddy soil on heavy metal availability and their uptake by rice plants

The experiments were done to investigate the effect of soil pH and organic matter content on EDTA-extractable heavy metal contents in soils and heavy metal concentrations in rice straw and grains. EDTA-extractable Cr contents in soils and concentrations in rice tissues were negatively correlated with soil pH, but positively correlated with organic matter content. The combination of soil pH and organic matter content would produce the more precise regression models for estimation of EDTA-Cu, Pb and Zn contents in soils, demonstrating the distinct effect of the two factors on the availability of these heavy metals in soils. Soil pH greatly affected heavy metal concentrations in rice plants. Furthermore, inclusion of other soil properties in the stepwise regression analysis improved the regression models for predicting straw Fe and grain Zn concentrations, indicating that other soil properties should be taken into consideration for precise predicting of heavy metal concentrations in rice plants.     

Chemical behavior of Cd in rice rhizosphere

Chemical behavior of Cd in rice rhizosphere as affected or not by Pb was investigated. The NH4OAc extractable Cd in the rhizosphere was distinctly lower than that in bulk soil. The depletion of Cd in the rhizosphere could not be simply attributed to Cd uptake by rice. The observed phenomena could be attributed to the decreasing pH in the rhizosphere and the complexing capabilities of soluble exudates for Cd. Extractable Cd increased in both the rhizosphere and bulk soil after the addition of Pb, which might be caused by the replacement of Pb for Cd. The extractable Cd in the non-rhizosphere varied with the distance from the root surface, especially within 0-1 mm, which was greatly affected by the combined effects of mass flow, activation and fixation, and had the lowest extractable Cd. Pb addition affected the distribution of extractable Cd in the non-rhizosphere, implying that the affinity of Pb for organic matter was greater than that of Cd. The difference of Cd species between rhizosphere and bulk soil demonstrated that the transformation of exchangeable Cd (EXC-Cd) to OM-Cd (bound to organic matter) and FMO-Cd (bound to iron and manganese oxide) occurred in the rice rhizosphere due to the exudations from the rice root, the activity of microorganisms on the root surface and the activation of Fe and Mn oxides. The interaction between Pb and Cd resulted in the content of EXC-Cd being higher in the presence of Pb, whereas the OM-Cd content was lower in the presence of Pb.     

Partitioning of arsenic in soil-crop systems irrigated using groundwater: a case study of rice paddy soils in southwestern Taiwan

The accumulation of As in rice due to groundwater irrigation in paddy fields represents a serious health hazard in South and Southeast Asia. In Taiwan, the fate of As in long-term irrigated paddy fields is poorly understood. Groundwater, surface soil, and rice samples were collected from a paddy field that was irrigated with As-containing groundwater in southwestern Taiwan. The purpose of this study is to elucidate the source and sink of As in the paddy field by comparing the As fractions in the soils that were obtained by a sequential extraction procedure (SEP) with the As uptake of rice. The risks associated with eating rice from the field can thus be better understood. The concentration of As in groundwater varied with time throughout the growing seasons of rice, but always exceeded the permitted maximum (10 μg L⁻¹) for drinking water by the WHO. The As concentration increased with the concentration of Fe in the groundwater, supporting the claim that a large amount of As was concentrated in the Fe flocs collected from the internal wall of the groundwater pump. The results of the SEP revealed that As bound with amorphous and crystalline hydrous oxides exhibited high availability in the soils. The root of rice accumulated the largest amount of As, followed by the straw, husk, and grain. Although the As concentration in the rice grain was less than 1.0 mg kg⁻¹, the estimated intake level was close to the maximum tolerable daily intake of As, as specified by the WHO.     

Short-term effects of compost amendment on the fractionation of cadmium in soil and cadmium accumulation in rice plants

Purpose

We used a sequential extraction to investigate the effects of compost amendment on Cd fractionation in soil during different incubation periods in order to assess Cd stabilization in soil over time.

Methods

Pot experiments using rice plants growing on Cd-spiked soils were carried out to evaluate the influence of compost amendment on plant growth and Cd accumulation by rice. Two agricultural soils (Pinchen and Lukang) of Taiwan were used for the experiments. The relationship between the redistribution of Cd fractions and the reduction of plant Cd concentration due to compost amendment was then investigated.

Results and discussion

Compost amendment in Pinchen soil (lower pH) could transform exchangeable Cd into the Fe- and Mn-oxide-bound forms. With increasing incubation time, exchangeable Cd tended to transform into carbonate- and Fe- and Mn-oxide-bound fractions. In Lukang soil (higher pH), carbonate- and Fe- and Mn-oxide-bonded Cd were the main fractions. Exchangeable Cd was low. Compost amendment transformed the carbonate-bound form into the Fe and Mn oxide form. Pot experiments of rice plants showed that compost amendment enhanced plant growth more in Pinchen soil than in Lukang soil. Compost amendment could significantly reduce Cd accumulation in rice roots in both Pinchen and Lukang soils and restrict internal transport of Cd from the roots to the shoots. Because exchangeable Cd can be transformed into the stronger bonded fractions quickly in Pinchen soil, a reduction of Cd accumulation in rice due to compost amendment of Pinchen soil was significant by 45?days of growth. However, carbonate-bonded fractions in Lukang soil may provide a source of available Cd to rice plants, and exchangeable and carbonate-bonded fractions are transformed into the other fractions slowly. Thus, reduction of Cd accumulation by rice due to compost amendment in Lukang soil was significant by 75?days of growth.

Conclusions

The results of the study suggest that the effectiveness of compost amendment used for stabilization of Cd and to decrease the phytoavailability of Cd for rice plants is different in acidic and alkaline soils. In acidic soil, Cd fractionation redistributes quickly after compost amendment and shows a significant reduction of Cd accumulation by the plant within a few weeks. In alkaline soil, due to the strongly bound fractions of Cd being in greater quantity than the weakly bound ones, a longer period (a few months) to redistribute Cd fractions is needed.     

Phytoavailability and extractability of potassium,magnesium and manganese in calcareous soil amended with olive oil wastewater

Abstract

Land disposal of olive oil wastewater using it as a soil amendment requires a knowledge of the effects that its application may produce on the status of the mineral nutrients in the plant‐soil system. A pot experiment using calcareous soil was performed in a growth chamber to examine the effects of olive oil wastewater on the availability and postharvest soil extractability of K, Mg and Mn. The experiment included 6 treatments: two rates of olive oil wastewater, two mineral fertilizer treatments containing K (which supplied K in amounts equivalent to the K supplied by the olive oil wastewater treatments), a K‐free mineral fertilizer treatment, and a control. The pots were sown with ryegrass as the test plant, harvesting 3 times at intervals of one month. Olive oil wastewater has demonstrated a considerable capacity for supplying K that can be assimilated by the plant, tending in fact to surpass the mineral potassium fertilizer tested. The application of olive oil wastewater tends to reduce the concentration of Mg in the plant, similarly to the effect of adding mineral potassium fertilizer. An enhancement of Mn availability takes place in the soil amended with olive oil wastewater, which on occasion has produced Mn concentrations in plant that could be considered phytotoxic or at least excessive. After harvesting, we observed an increase in the amount of exchangeable K in soil with added industrial wastewater. However, these increases are lower than those in soil treated with mineral potassium fertilizer. The levels of exchangeable, carbonate‐bound, organic‐bound and residual Mg in soil were higher in treatments incorporating olive oil wastewater than in those with added mineral K, with the opposite tendency occurring in the amount of Fe‐Mn oxides‐bound Mg in soil. Treatments based on olive oil wastewater, especially in high doses, increased the amount of exchangeable and carbonate‐bound Mn in soil, in comparison with treatments adding mineral fertilizers with or without K. In contrast, the addition of industrial wastewater caused a drop in the amount of Fe‐Mn oxides‐bound and organic‐bound Mn in soil.     

Leaching and reduction of chromium in soil as affected by soil organic content and plants

The oxidation state of chromium in contaminated soils is an important indicator of toxicity and potential mobility. Chromium in the hexavalent state is highly toxic and soluble, whereas the trivalent state is much less toxic and relatively insoluble. A laboratory study investigated the impact of growing plants and supplemental organic matter on chromium transport in soil. Plants alone had no appreciable effect on the chromium oxidation state in soil. Soil columns with higher organic content were associated with lower ratios of chromate:total chromium than the columns with lower organic matter. Analyses of column leachate, plant biomass, and soil indicate that more chromium leaching occurred in the vegetated, low organic columns. Retention of Cr in the soils was correlated to the Cr(III) content. Plant uptake of chromium accounted for less than 1% of the chromium removed from the soil. Overall, the addition of organic matter had the strongest influence on chromium mobility.     

北运河沉积物/水界面上重金属迁移转化规律

分析测定了6种元素(Cr、Co、Mn、Cu、Pb、Zn)在北运河水系10个采样点水体和表层沉积物中的含量和形态分布,利用SPSS 19.0统计软件对重金属在不同形态中的含量进行相关性分析。结果显示,北运河下游重金属污染程度高于上游;Cr、Cu、Pb、Zn在底泥可提取态中所占比例相当高,多数采样点都超过10.0%。所研究的重金属多数在底泥Fe-Mn结合态与悬浮物、可交换态、硫化物和有机质结合态均存在相关性;Mn是北运河地化循环中最为活跃的元素。     

Use of sequential extraction to assess metal partitioning in soils

The state of heavy metal pollution and the mobility of Cd, Cu, Ni, Cr, Pb and Zn were studied in three texturally different agricultural soil profiles near a Cu-Ni smelter in Harjavalta, Finland. The pseudo-total concentrations were determined by an aqua regia procedure. Metals were also determined after division into four fractions by sequential extraction with (1) acetic acid (exchangeable and specifically adsorbed metals), (2) a reducing agent (bound to Fe/Mn hydroxides), (3) an oxidizing agent (bound to soil organic matter) and (4) aqua regia (bound to mineral structures). Fallout from the smelter has increased the concentrations of Cd, Cu and Ni in the topsoil, where 75-90% of Cd, 49-72% of Cu and 22-52% of Ni occurred in the first two fractions. Slight Pb and Zn pollution was evident as well. High proportions of mobile Cd, Cu and Ni also deeper in the sandy soil, closest to the smelter, indicated some downward movement of metals. The hydroxide-bound fraction of Pb dominated in almost all soils and horizons, while Ni, Cr and Zn mostly occurred in mineral structures. Aqua regia extraction is usefully supplemented with sequential extraction, particularly in less polluted soils and in soils that exhibit substantial textural differences within the profiles.     

Distribution and Fractionation of Copper in Soils of Apple Orchards (5 pp)

Background Frequent application of Bordeaux mixture, which includes copper, as a fungicide in fruit and grape orchards may lead to copper accumulation in the soil, especially when orchard age and application times increase. The objectives of this study were: (i) to investigate the copper content and its spatial distribution in orchard soils; (ii) to identify the copper fractionation in soil and its relationship with plant uptake; (iii) to understand the characteristics of copper contamination in orchard soils. Materials and Methods Soil profile samples were taken in apple orchards with ages of 0, 5, 10, 20, 30 years and pot experiments were also carried out to study the effects of external copper input on copper fractionation. All soil samples were air-dried, ground and extracted with 0.43 mol L–1 HNO3 for the total absorbed copper. Fractionation determination was conducted following Tessier and Shuman sequential extraction methods, and copper was measured with AAS. Plant samples were first dry ashed, dissolved with 6 mol L–1 HCl and then copper and other elements were measured with ICP-MS.Results and Discussion Soil total Cu was higher in the apple orchards than that in non-orchard fields and was seen to have increased with orchard age. Soil Cu increased substantially with the average annual copper increase, ranging from 2.5 to 9 mg Cu kg–1. The distribution of copper in the soil profile was uneven, decreasing from surface to deeper layers, and the differences were significant, but the contents in every layer were also significantly correlated with those in the next layers. For all copper fractions, the organically bound, crystalline Mn oxide bound, and amorphous Fe bound fractions extracted with the Shuman method were much higher than the exchangeable and residual fractions. Using the Tessier method, organically bound, carbonate bound and Fe-Mn oxide bound fractions were much higher. With an increase in external copper input, the organically bound, crystalline Mn oxide bound and amorphous Fe bound fractions in the Shuman method and organically bound, carbonate bound and Fe-Mn oxide bound fractions in the Tessier method all increased significantly, while the changes in other fractions were not significant. Soil total copper and copper fractions were found to have good correlations with apple tree uptake. Copper in fruit flesh had significant correlations with soil total content in the 0–10 cm layer, all the copper fractions in the 0–5 cm layer, and some fractions in the deeper layers. Conclusion Copper content in orchard soils increased significantly with intensive application of Bordeaux mixtures and orchard age. Copper content decreased sharply from the topsoil to deeper soil layers. The copper contents in different layers also significantly correlated with those in the next layers. Dominant fractions of the copper in soil were mainly associated with organic matter, iron and manganese oxides and carbonates. A close relationship was found between the copper content in soils and in apple tree organs (which contained 8.9 to 66mg kg–1 Cu). Recommendation and Perspective Though most copper in the soil was specifically adsorbed or immobilized, and copper was mainly distributed in topsoil, which was essentially devoid of roots, the copper concentration of fruit still had significantly positive correlations with soil copper and most copper fractions. Therefore, measures must be taken to control copper accumulation in orchard soils and to make the apple fruit production sustainable.