Phytoremediation of pyrene contaminated soils amended with compost and planted with ryegrass and alfalfa

Ryegrass (Lolium perenne) and alfalfa (Medicago sativa) were planted in pots to remediate pyrene contaminated quartz sand (as a control group), alluvial and red soils amended with and without compost. The pyrene degradation percentages in quartz sand, alluvial soil, and red soil amended with compost (5%, w/w) and planted with ryegrass and alfalfa for 90 d growth were 98-99% and 97-99%, respectively, while those of pyrene in the corresponding treatments amended without compost but planted with ryegrass and alfalfa were 91-96% and 58-89%, respectively. Further, those of pyrene in the respective treatments amended with and without compost but unplanted were 54-77% and 51-63%, respectively. Pyrene contents in both roots and aboveground parts of ryegrass and alfalfa after 90 d growth in quartz sand and the two soils amended with or without compost were trace amounts. Statistical analyses for the parameters of ryegrass planted in red and alluvial soils including the concentrations of total water-soluble volatile low molecular weight organic acids, microbial population, pyrene degradation percentage, and spiked pyrene concentration show significant correlations at 5% and mostly 1% probability levels, by the analysis of variance. It was thus suggested that the interactions among the consortia of plant root exudates, microorganisms, and amended compost in rhizosphere soils could facilitate bioavailability of pyrene and subsequently enhance its dissipation.     

Residues of chlorantraniliprole in rice field ecosystem

The fate of chlorantraniliprole was studied in rice field ecosystem, and a simple and reliable analytical method was developed for determination of chlorantraniliprole in soil, rice straw, paddy water and brown rice. Chlorantraniliprole residues were extracted from samples with acetonitrile. The extract was cleaned up with QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method, and determined by high-performance liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS). The average recoveries were 76.9-82.4% from soil, 83.6-89.3% from rice straw, 95.2-103.1% from paddy water and 84.9-87.7% from brown rice. The relative standard deviation was less than 15%. The limits of detection (LODs) of chlorantraniliprole calculated as a sample concentration (S/N ratio of 3) were 0.012 μg L(-1) for paddy water, 0.15 μg kg(-1) for soil, brown rice and rice straw. The results of the kinetics study of chlorantraniliprole residue showed that chlorantraniliprole degradation in soil, water and rice straw coincided with C=0.01939e(-0.0434t), C=0.01425e(-0.8111t), and C=1.171e(-0.198t), respectively; the half-lives were about 16.0 d, 0.85 d and 3.50 d, respectively. The degradation rate of chlorantraniliprole in water was the fastest, followed by rice straw. The final residues of chlorantraniliprole on brown rice were lower than maximum residue limit (MRL) of 0.02 mg kg(-1) after 14 d Pre-Harvest Interval (PHI). Therefore, a dosage of 150 mL a.i.hm(-2) was recommended, which could be considered as safe to human beings and animals.     

Fate of anilide and aniline herbicides in plant-materials-amended soils

The fate of herbicides trifluralin, pendimethalin, alachlor and metolachlor in paddy field soils amended with plant materials was investigated. The plant materials were purple sesbania, vegetable soybean and rice straw. The investigation was performed at two temperatures (25 and 40 degrees C) and two soil water moistures (60 and 90% water-holding capacity). The results showed linear and Freudlich equations described the adsorption of amide compound to soil. Adsorption coefficient (K(d)) fit to linear equation were in general greater in plant material-amended soils than in non-amended soil, especially in soil amending with rice straw. Increasing temperature and soil water moisture content shortened the half-lives of compounds in various treated soils. The movement of compounds in the soil columns showed the maximum distribution of aniline type compound, trifluralin and pendimethalin, appeared at the upper top of 0 to 5 and 0 to 10 cm of soil column, respectively, and of anilide type, alachlor and metolachlor, were distributed at 0 to 25 cm of the soil column. The mobility of chemicals in the different treated soils was simulated by the behavior assessment model (BAM). There was no significant difference among different plant material incubated soils on dissipation and mobility of compounds in soils.     

Carbon deposition in soil rhizosphere following amendments with compost and its soluble fractions, as evaluated by combined soil-plant rhizobox and reporter gene systems

We determined the organic carbon released by roots of maize plants (Zea mays L.) when grown in soils amended with compost and its soluble fractions. In rhizobox systems, soil and roots are separated from the soil of a lower compartment by a nylon membrane. Treatments are applied to the upper compartment, while in the lower compartment luminescent biosensors measure the bioavailable organic carbon released by roots (rhizodeposition). The rhizobox-plants systems were amended with a compost (COM), its water extract (TEA), the hydrophobic (HoDOM) and hydrophilic (HiDOM) fractions of the dissolved organic matter (DOM) extracted from the compost. After root development, the lower untreated compartments were sampled and sliced into thin layers. The bioavailable organic carbon in each layer was assessed with the lux-marked biosensor Pseudomonas fluorescens 10586 pUCD607, and compared with total organic carbon (TOC) analyses. The TOC values ranged between 8.4 and 9.6 g kg(-1) and did not show any significant differences between bulk and rhizosphere soil samples in any treatment. Conversely, the biosensor detected significant differences in available C compounds for rhizosphere soils amended with various organic materials. Concentrations of available organic compounds in the first 2 mm of soil rhizosphere were 1.69 (control), 1.09 (COM), 2.87 (HiDOM), 4.73 (HoDOM) and 2.14 (TEA)micromol Cg(-1) soil g(-1) roots. The applied rhizobox-biosensor integrated method was successful in detecting and quantifying effects of organic amendments on organic carbon released by maize plant roots. This approach may become important in assessing the carbon cycle in agricultural soils and soil-atmosphere compartments.     

In situ immobilization of Cu(II) in soils using a new class of iron phosphate nanoparticles

This study tested the feasibility of using a new class of iron phosphate (vivianite) nanoparticles synthesized using sodium carboxymethyl cellulose (NaCMC) as a stabilizer for in situ immobilization of Cu(II) in soils. Transmission electron microscopy measurements demonstrated that the particle size was about 8.4+/-2.9 nm. Batch tests showed that nano-sized vivianite particles can effectively reduce the leachability and in vitro bioaccessibility of Cu(II) in three representative soils (calcareous, neutral, and acidic) at the low doses of 0.61 and 3.01 mg PO(4) g(-1) soil. The Cu leachability was evaluated by the toxicity characteristic leaching procedure and in vitro bioaccessibility was evaluated by the physiological based extraction test. In the case of soil amendment with nanoparticles in 3.01 mg PO(4) g(-1) soil, Cu leachability reduced 63-87% and Cu concentrations in TCLP extract decreased from 1.74-13.33 mg l(-1) to 0.23-2.55 mg l(-1) after those soils were amended for 56 d. Meanwhile, the bioaccessibility of Cu was reduced by 54-69%. Sequential extraction procedures showed the significant decrease of water soluble/exchangeable Cu(II) and carbonate bound fractions and concomitant increase of Cu residual fraction after the soils were amended with the nanoparticles, suggesting that the formation of copper phosphate minerals through precipitation and adsorption was probably responsible for the decrease of Cu availability in soils. Visual MINTEQ modeling further revealed that Cu(3)(PO(4))(2) and Cu(5)(PO(4))(3)OH were formed in the vivianite-solid Cu(II) system, resulting in the decreased solubility of the Cu(II) in the acidic pH range.     

Fate of Bacillus thuringiensis (Bt) Cry3Bb1 protein in a soil microcosm

Transgenic crops expressing insecticidal, crystalline (Cry) Bacillus thuringiensis (Bt) proteins were commercialized in the US in 1996. There is little information in the peer-reviewed literature on the environmental fate of the coleopteran-active Bt Cry3Bb1 protein expressed in event MON863 corn. The exposure characterization of Bt proteins is unique in that the fate of the protein in soil and in crop residue must be considered. To date, the significance of macrodecomposing organisms, such as earthworms, isopods, and springtails, to the dissipation of Bt proteins present in crop residue has not been assessed. In addition, the input of Bt proteins into soil through leaching from post-harvest crop residue has not been examined. Two laboratory microcosm studies were conducted to determine the fate of Bt Cry3Bb1 in decomposing MON863 corn residue and to determine whether Bt proteins can enter soil by leaching from crop residue. In addition, the importance of macrodecomposing organisms to the degradation of Bt proteins in corn residue was assessed. Laboratory microcosms containing MON863 corn leaf, root, and stalk with and without macrodecomposers were used to examine the fate of Bt Cry3Bb1 in post-harvest MON863 corn residue. A half-life of less than five days was found for Bt Cry3Bb1 protein in decomposing MON863 corn residue. There was a trend of increasing half-life of Cry3Bb1 in microcosms containing macrodecomposers, however, this trend was only significant (p<0.05) for Bt Cry3Bb1 in MON863 leaf tissue and this increase is not likely relevant for non-target exposure. The recovery of Bt Cry3Bb1 protein from soil extracts was either below the limit of quantification (9 ng g(-1) soil) or below the limit of detection (0.7 ng mL(-1)) at all time points during the study. Based on the results from this study, Bt protein leaching from post-harvest crop residue is not a significant contributor to Bt protein input into soil.     

Concentration and dissipation of chlorantraniliprole and thiamethoxam residues in maize straw,maize, and soil

To study the dissipation rates and final residual levels of chlorantraniliprole and thiamethoxam in maize straw, maize, and soil, two independent field trials were conducted during the 2014 cropping season in Beijing and Anhui Provinces of China. A 40% wettable powder (20% chlorantraniliprole?+?20% thiamethoxam) was sprayed onto maize straw and soil at an application rate of 118 g of active ingredient per hectare (g a.i.ha^?1). The residual concentrations were determined by ultra-high-performance liquid chromatography–tandem mass spectrometry. The chlorantraniliprole half-lives in maize straw and soil were 9.0–10.8 and 9.5–21.7 days, respectively. The thiamethoxam half-lives in maize straw and soil were 8.4–9.8 and 4.3–11.7 days, respectively. The final residues of chlorantraniliprole and thiamethoxam in maize straw, maize, and soil were measured after the pesticides had been sprayed two and three times with an interval of 7 days using 1 and 1.5 times the recommended rate (72 g a.i. ha^?1 and 108 g a.i. ha^?1, respectively). Representative maize straw, maize, and soil samples were collected after the last treatment at pre-harvest intervals of 7, 14, and 28 days. The chlorantraniliprole residue was below 0.01 mg kg^?1 in maize, between 0.01 and 0.31 mg kg^?1 in maize straw, and between 0.03 and 1.91 mg kg^?1 in soil. The thiamethoxam residue concentrations in maize, maize straw, and soil were <0.01, <0.01, and 0.01–0.03 mg kg^?1, respectively. The final pesticide residues on maize were lower than the maximum residue limit (MRL) of 0.02 mg kg^?1 after a 14-day pre-harvest interval. Therefore, a dosage of 72 g a.i. ha^?1 was recommended, as it can be considered safe to human beings and animals.     

Residues and dynamics of probenazole in rice field ecosystem

The simple and efficient method for determination of probenazole in soil, rice plant, and paddy water was developed, and the fate of probenazole in rice field ecosystem was also studied. Probenazole residues were extracted from sample, cleaned up by liquid/liquid partition and chromatographic column and then determined by gas chromatography with flame photometric detection. As far as the accuracy and precision was concerned, the method met certain standard. The LODs of probenazole calculated as a sample concentration (S/N ratio of 3) was 0.02 mg kg-1. The minimum detectable limit was 5x10(-10) g. The degradation of probenazole in soil, rice straw, and water was determined. The results showed that probenazole degradation in soil and rice straw coincided with C=0.576e-0.147t, C=17.858e-0.414t, respectively; the half-lives were about 4.7 and 1.7 d, respectively. The degradation rate of probenazole in rice straw was faster than that of in soil. Probenazole residue at 0.02 mg kg-1 could only be detected in paddy water within the first day after application. The final probenazole residues in soil, brown rice, and water were undetectable at levels of recommended and doubled dosage with an interval of 63 d. Therefore, a dosage of 1800-3600 g a.i. hm-2 was recommended, which could be considered as safe to human beings and animals. These would contribute to provide the scientific basis of using this fungicide.     

Fate of anilide and aniline herbicides in plant-materials-amended soils

The fate of herbicides trifluralin, pendimethalin, alachlor and metolachlor in paddy field soils amended with plant materials was investigated. The plant materials were purple sesbania, vegetable soybean and rice straw. The investigation was performed at two temperatures (25 and 40°C) and two soil water moistures (60 and 90% water-holding capacity). The results showed linear and Freudlich equations described the adsorption of amide compound to soil. Adsorption coefficient (K _d ) fit to linear equation were in general greater in plant material-amended soils than in non-amended soil, especially in soil amending with rice straw. Increasing temperature and soil water moisture content shortened the half-lives of compounds in various treated soils. The movement of compounds in the soil columns showed the maximum distribution of aniline type compound, trifluralin and pendimethalin, appeared at the upper top of 0 to 5 and 0 to 10 cm of soil column, respectively, and of anilide type, alachlor and metolachlor, were distributed at 0 to 25 cm of the soil column. The mobility of chemicals in the different treated soils was simulated by the behavior assessment model (BAM). There was no significant difference among different plant material incubated soils on dissipation and mobility of compounds in soils.     

Poor efficacy of herbicides in biochar-amended soils as affected by their chemistry and mode of action

We evaluated wheat straw biochar produced at 450 °C for its ability to influence bioavailability and persistence of two commonly used herbicides (atrazine and trifluralin) with different modes of action (photosynthesis versus root tip mitosis inhibitors) in two contrasting soils. The biochar was added to soils at 0%, 0.5% and 1.0% (w/w) and the herbicides were applied to those soil-biochar mixes at nil, half, full, two times, and four times, the recommended dosage (H₄). Annual ryegrass (Lolium rigidum) was grown in biochar amended soils for 1 month. Biochar had a positive impact on ryegrass survival rate and above-ground biomass at most of the application rates, and particularly at H₄. Within any given biochar treatment, increasing herbicide application decreased the survival rate and fresh weight of above-ground biomass. Biomass production across the biochar treatment gradient significantly differed (p < 0.01) and was more pronounced in the case of atrazine than trifluralin. For example, the dose-response analysis showed that in the presence of 1% biochar in soil, the value of GR₅₀ (i.e. the dose required to reduce weed biomass by 50%) for atrazine increased by 3.5 times, whereas it increased only by a factor of 1.6 in the case of trifluralin. The combination of the chemical properties and the mode of action governed the extent of biochar-induced reduction in bioavailability of herbicides. The greater biomass of ryegrass in the soil containing the highest biochar (despite having the highest herbicide residues) demonstrates decreased bioavailability of the chemicals caused by the wheat straw biochar. This work clearly demonstrates decreased efficacy of herbicides in biochar amended soils. The role played by herbicide chemistry and mode of action will have major implications in choosing the appropriate application rates for biochar amended soils.     

Behaviour of simazine in soil amended with the final residue of the olive-oil extraction process

Addition of organic wastes to agricultural soils is becoming a common practice as a disposal strategy and to improve the physical and chemical soil properties. However, in order to optimise the use of organic wastes as soil amendments, their effect on the behaviour of other compounds that are also used in agriculture, such as pesticides, needs to be assessed. In this work, we have investigated the effects of the addition of the final solid residue of the new technology of olive-oil extraction (extracted alperujo or solid olive-mill waste, SOMW2) on the sorption, degradation and leaching of the herbicide simazine in a sandy loam soil. The results are compared with those of a previous study, where the intermediary by-product of the olive-oil processing technology (unextracted alperujo or SOMW1) was applied to the same soil. The soil was amended in the laboratory with SOMW2 at two different rates (5% and 10% w/w). Simazine sorption isotherms showed a great increase in herbicide sorption after SOMW2 addition to soil. SOMW2 addition also increased sorption irreversibility. Incubation studies revealed reduced biodegradation of simazine in the soil amended with SOMW2 compared to the unamended soil. Breakthrough curves of simazine in handpacked soil columns showed that SOMW2 addition retarded the vertical movement of the herbicide through the soil and greatly reduced the amount of herbicide available for leaching. Interestingly, the results were quantitatively different from those obtained for the intermediary by-product SOMW1, illustrating the importance of the specific characteristics of the organic amendment in determining its effect on pesticide behaviour.     

Rapid degradation of butachlor in wheat rhizosphere soil

The degradative characteristics of butachlor in non-rhizosphere, wheat rhizosphere, and inoculated rhizosphere soils were measured. The rate constants for the degradation of butachlor in non-rhizosphere, rhizosphere, and inoculated rhizosphere soils were measured to be 0.0385, 0.0902, 0.1091 at 1 mg/kg, 0.0348, 0.0629, 0.2355 at 10 mg/kg, and 0.0299, 0.0386, 0.0642 at 100 mg/kg, respectively. The corresponding half-lives for butachlor in the soils were calculated to be 18.0, 7.7, 6.3 days at 1 mg/kg, 19.9, 11.0, 2.9 days at 10 mg/kg, and 23.2, 18.0, 10.8 days at 100 mg/kg, respectively. The experimental results show that the degradation of butachlor can be enhanced greatly in wheat rhizosphere, and especially in the rhizosphere inoculated with the bacterial community designated HD which is capable of degrading butachlor. It could be concluded that rhizosphere soil inoculated with microorganisms-degrading target herbicides is a useful pathway to achieve rapid degradation of the herbicides in soil.     

Heavy metal immobilization by chemical amendments in a polluted soil and influence on white lupin growth

The effects of chemical amendments (zeolite, compost and calcium hydroxide) on the solubility of Pb, Cd and Zn in a contaminated soil were determined. The polluted soil was from the Southwest Sardinia, Italy. It showed very high total concentrations of Pb (19663 mgkg(-1) d.m.), Cd (196 mgkg(-1) d.m.) and Zn (14667 mgkg(-1) d.m.). The growth and uptake of heavy metals by white lupin (Lupinus albus L., cv. Multitalia) in amended soils were also studied in a pot experiment under greenhouse conditions. Results showed that the amendments increased the residual fraction of heavy metals in the soils, and decreased the heavy metals uptake by white lupin compared with the unamended control. Among the three amendments, compost and Ca(OH)2 were the most efficient at reducing Pb and Zn uptake, while zeolite was the most efficient at reducing Cd uptake by the plants. White lupin growth was better in amended soils than in unamended control. The above ground biomass increased with a factor 1.8 (soil amended with zeolite), 3.6 (soil amended with compost) and 3.1 (soil amended with Ca(OH)2) with respect to unamended soil. The roots biomass increased with a factor 1.4 (soil amended with zeolite), 5.6 (soil amended with compost) and 4.8 (soil amended with Ca(OH)2). Results obtained suggest that the soil chemical treatment improved the performance of crops by reducing bioavailability of metals in the soils. However it would be therefore interesting to find a suitable mixture of these amendments to contemporarily immobilize the three main pollutants in the polluted soils.     

不同镉污染农田土壤上秸秆和炭化秸秆分解动态及其对土壤镉的吸附特征

通过温室土壤培养实验,研究不同镉污染农田土壤上不同的作物秸秆和炭化作物秸秆还田后的分解动态和还田秸秆材料对污染土壤中镉的吸附特征,探讨秸秆和炭化秸秆还田做为重金属镉污染农田土壤修复剂的可行性。实验结果表明,还田的油菜秸秆和玉米秸秆在2种镉污染水稻土壤上6个月分解了43％-65％,秸秆炭化后还田则很稳定,2种镉污染土壤上还田6个月时累计分解量小于5％。2种镉污染土壤上还田的秸秆和炭化秸秆随还田时间延长镉含量逐渐增加。模拟镉污染土壤上,相同时期油菜秸秆中镉含量显著高于玉米秸秆,油菜秸秆炭中镉含量显著高于玉米秸秆炭。在镉污染土壤上,还田的玉米秸秆、油菜秸秆、玉米秸秆炭和油菜秸秆炭对土壤镉的净吸附量相近,均小于1．1μg／g。在模拟镉污染土壤上还田的油菜秸秆和油莱秸秆炭对土壤镉净吸附量最高分别达到2．74μg／g和7．03μg／g,分别是玉米秸秆和玉米秸秆炭的2倍,且显著高于其在镉污染土壤上的净吸附量,具有高的吸附能力。     

Influence of salinity on bioremediation of oil in soil

Spills from oil production and processing result in soils being contaminated with oil and salt. The effect of NaCl on degradation of oil in a sandy-clay loam and a clay loam soil was determined. Soils were treated with 50 g kg(-1) non-detergent motor oil (30 SAE). Salt treatments included NaCl amendments to adjust the soil solution electrical conductivities to 40, 120, and 200 dS m(-1). Soils were amended with nutrients and incubated at 25 degrees C. Oil degradation was estimated from the quantities of CO(2) evolved and from gravimetric determinations of remaining oil. Salt concentrations of 200 dS m(-1) in oil amended soils resulted in a decrease in oil mineralized by 44% for a clay loam and 20% for a sandy-clay loam soil. A salt concentration of 40 dS m(-1) reduced oil mineralization by about 10% in both soils. Oil mineralized in the oil amended clay-loam soil was 2-3 times greater than for comparable treatments of the sandy-clay loam soil. Amending the sandy-clay loam soil with 5% by weight of the clay-loam soil enhanced oil mineralization by 40%. Removal of salts from oil and salt contaminated soils before undertaking bioremediation may reduce the time required for bioremediation.     

The impact of synthetic pyrethroid and organophosphate sheep dip formulations on microbial activity in soil

Sheep dip formulations containing organophosphates (OPs) or synthetic pyrethroids (SPs) have been widely used in UK, and their spreading onto land has been identified as the most practical disposal method. In this study, the impact of two sheep dip formulations on the microbial activity of a soil was investigated over a 35-d incubation. Microbial utilisation of [1-(14)C] glucose, uptake of (14)C-activity into the microbial biomass and microbial numbers (CFUs g(-1) soil) were investigated. In control soils and soils amended with 0.01% sheep dip, after 7d a larger proportion of added glucose was allocated to microbial biomass rather than respired to CO(2). No clear temporal trends were found in soils amended with 0.1% and 1% sheep dips. Both sheep dip formulations at 0.1% and 1% concentrations resulted in a significant increase in CFUs g(-1) soil and [1-(14)C] glucose mineralisation rates, as well as a decline in microbial uptake of [1-(14)C] glucose, compared to control and 0.01% SP- or OP-amended soils. This study suggests that the growth, activity, physiological status and/or structure of soil microbial community may be affected by sheep dips.     

Degradation of monocrotophos in soils

The degradation of a widely used organophosphorus insecticide, monocrotophos (dimethyl (E)-1-methyl-2-methylcarbamoyl vinyl phosphate) in two Indian agricultural soils at two concentration levels, 10 and 100 microg g(-1) soil under aerobic conditions at 60% water-holding capacity at 28+/-4 degrees C was studied in a laboratory. The degradation of monocrotophos at both concentrations in black vertisol and red alfinsol soils was rapid accounting for 96-98% of the applied quantity and followed the first-order kinetics with rate constants (k) of 0.0753 and 0.0606 day(-1) and half-lives (t1/2) of 9.2 and 11.4 days, respectively. Degradation of monocrotophos in soils proceeded by hydrolysis with formation of N-methylacetoacetamide. Even three additions of monocrotophos at 10 microg g(-1) soil did not result in its enhanced degradation. However, there was cumulative accumulation of N-methylacetoacetamide in soils pretreated with monocrotophos to the tune of 7-15 microg g(-1) soil. Both biotic and abiotic factors were involved in degradation of monocrotophos in soils.     

Bioavailability of selenium to forage crops in a sandy loam soil amended with Se-rich plant materials

Greenhouse experiments were conducted to study the bioavailability of selenium (Se) to sorghum (Sorghum bicolor L.), maize (Zea mays L.) and berseem (Trifolium alexandrinum L.) fodders in a sandy loam soil amended with different levels of Se-rich wheat (Triticum aestivum L.) and raya (Brassica juncea L. Czern) straw containing 53.3 and 136.7microg Seg(-1), respectively. Each of the fodder crops was grown after incorporation of Se-rich materials either individually or in a sequence - sorghum-maize-berseem by incorporating Se-rich straws only to the first crop. Application of Se-rich straws to each crop, even at the greatest rate of 1%, did not have any detrimental effect on dry matter yield of different crops. With increase in the level of wheat straw from 0% to 1%, Se content in sorghum and maize plants increased to greatest level of 1.3 and 1.5microg g(-1), respectively, at 0.3% of applied straw and thereafter it decreased consistently. In case of raya straw, the greatest Se content in sorghum (2.3microg g(-1)) and maize (3.0microg g(-1)) was recorded at 0.3% and 0.4% of the applied straw, respectively. Unlike sorghum and maize fodders, Se content in all the four cuts of berseem continued to increase with increase in the level of applied straws and for different cuts of berseem it varied from 1.6 to 2.3 and 3.4 to 4.3microg g(-1) in case of wheat and raya straw, respectively. Similar variations in Se content of different fodder crops were recorded when these were grown in the sequence - sorghum-maize-berseem; but Se content was 2-4 times lower than when each crop was grown with fresh application of Se-rich straw. None of the fodders absorbed Se in levels toxic for animal consumption (>5microg g(-1)) even at the greatest level of applied straw. Of the total Se added through Se-rich straws, utilization of Se was not more than 2% in case of sorghum and maize crops and up to 5% in case of berseem. At the time of sowing of sorghum, hot water soluble Se (HWS-Se) in soils treated with different levels of Se-rich wheat and raya straw, respectively, varied from 18 to 36 and 18 to 79microg kg(-1). Whereas in case of berseem, it varied from 33 to 101 and 33 to 154microg kg(-1), respectively. HWS-Se present at the sowing time of berseem was significantly correlated with Se content of all the four cuts in the soil treated with Se-rich straws; the coefficients of correlation 'r' varied between 0.79 (p0.05) and 0.99 (p0.001). Selenium-rich materials supplied significant amounts of S, P and micronutrients to the growing fodder crops. These investigations suggest that Se-rich raya and wheat straw may be disposed off safely in soils used for growing fodders.     

Residues and dynamics of pymetrozine in rice field ecosystem

The fate of pymetrozine was studied in rice field ecosystem, and a simple and reliable analytical method for determination of pymetrozine in soil, rice straw, paddy water and brown rice was developed. Pymetrozine residues were extracted from samples, cleaned up by solid phase extraction (SPE) and then determined by high-performance liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS-MS). The average recovery was 81.2-88.1% from soil, 83.4-88.6% from rice straw, 87.3-94.1% from paddy water and 82.9-85.3% from brown rice. The relative standard deviation (RSD) was less than 15%. The limits of detection (LODs) of pymetrozine calculated as a sample concentration were 0.0003 mg kg⁻¹ (mg L⁻¹) for soil and paddy water, 0.001 mg kg⁻¹ for brown rice and rice straw. The results of kinetics study of pymetrozine residue showed that pymetrozine degradation in water, soil, and rice straw coincided with C = 0.194e^−0.986t, C = 0.044e^−0.099t, and C = 0.988e^−0.780t, respectively; the half-lives were about 0.70 d, 7.0 d and 0.89 d, respectively. The degradation rate of pymetrozine in water was the fastest, followed by rice straw. The highest final pymetrozine residues in brown rice were 0.01 mg kg⁻¹, which was lower than the EU’s upper limit of 0.02 mg kg⁻¹ in rice. Therefore, a dosage of 300-600 g a.i.hm⁻² was recommended, which could be considered as safe to human beings and animals.     

Comparison between fractionation and bioavailability of trace elements in rhizosphere and bulk soils

Rhizosphere is a microbiosphere and has quite different chemical, physical and biological properties from bulk soils. A greenhouse experiment was performed to compare the difference of fractionation and bioavailability of trace elements Cr, Ni, Zn, Cu, Pb and Cd between rhizosphere soil and bulk soil. In the meantime, the influence of air-drying on the fractionation and bioavailability was also investigated by using wet soil sample as a control. Soils in a homemade rhizobox were divided into four zones: rhizosphere, near rhizosphere, near bulk soil and bulk soil zones, which was designated as S1, S2, S3 and S4. Elemental speciations were fractionated to water soluble, exchangeable and carbonate bound (B1), Fe-Mn oxide bound (B2), and organic and sulfide bound (B3) by a sequential extraction procedure. Speciation differences were observed for elements Cr, Ni, Zn, Cu, Pb and Cd between the rhizosphere and bulk soils, and between the air-dried and wet soils as well. The concentrations of all six heavy metals in fraction B1 followed the order of S2 > S3 > S1 > S4 and for B2, the order was S2 > S3 S4 > S1. For B3, the order was S1 > S3 S4 > S2, while for Cd the order was S2 > S3 approximately/= S4 > S1. The air-drying increased elemental concentration in fractions B1 and B2 by 20-50% and decreased in fraction B3 by about 20-100%. Correlation analysis also indicated that the bioavailability correlation coefficient of fraction B1 in rhizosphere wet soil to plants was better than that between either air-dried or nonrhizosphere soils. Therefore, application of rhizosphere wet soils should be recommended in the future study on the speciation analysis of trace elements in soils and bioavailability.