Transformation and binding of 13C and 14C-labelled atrazine in relation to straw decomposition in soil

As a source of organic matter, crop residues affect the behaviour of pesticides in agricultural soils. The fate of [U‐ring‐¹³C] and [U‐ring‐¹⁴C] atrazine (6‐chloro‐N‐ethyl‐N‐isopropyl‐1,3,5‐triazine‐2,4‐diamine) was investigated during laboratory incubation under controlled conditions in a loamy soil amended with wheat straw at two different states of decomposition: no preliminary decomposition or 6 months’ preliminary decomposition. After 3 months, non‐extractable, so‐called ‘bound’, ¹³C‐atrazine residues were recovered in three particle‐size fractions (> 200, 50–200 and < 50 μm), and investigated with solid‐state ¹³C‐NMR spectroscopy. Parallel incubations with [U‐ring‐¹⁴C] atrazine were carried out to quantify the bound residues as well as the extractable and mineralized fractions. The effect of straw residues on atrazine behaviour depended on whether they had been previously decomposed or not. When straw was decomposed for 6 months prior to incubation, atrazine mineralization was enhanced to 50% of the initial ¹⁴C in contrast to 15% of the initial ¹⁴C in soil alone and soil amended with fresh straw. In parallel, atrazine bound residues were formed in greater amount representing up to 20% of the initial ¹⁴C. CP/MAS ¹³C‐NMR on soil size fractions of soil–straw mixtures after incubation with ¹³C‐atrazine showed that bound residues contained mostly triazinic C, corresponding to atrazine or primary metabolites. Non‐humified organic materials recovered in size fractions > 200 and 50–200 μm contained significant amounts of bound residues, especially when straw was added to the soil. CP/MAS ¹³C‐NMR analysis of humic acids obtained from < 50‐μm fractions was difficult due to overlapping of the native carboxyl ¹³C signal with the ¹³C‐atrazine signal.     

Chemical and colloidal stability of sols in the Al2O3-Fe2O3-SiO2-H2O system: their role in podzolization

Concentrations of dialysable silica in equilibrium with Al₂O₃-SiO₂-H₂O sols at pH 4.5–5.0 confirm the formation of a poorly ordered non-dialysable proto-imogolite species with an Al : Si ratio near 2, close to that of imogolite. Sols with Al : Si>2 give nearly constant levels of free silica in solution in the range 2–6 μg/cm³, indicating equilibrium between proto-imogolite and aluminium hydroxide species. These findings indicate that imogolite-like precipitates in acid soils will buffer silica in solution to within this range during leaching episodes. Imogolite is more stable than a previous estimate suggested, and a revised value for its free energy of formation is proposed: ΔG⁰_f(298.15) = -2929.7 kJ/mol. In Fe₂O₃-SiO₂-H₂O sols, the Fe : Si ratio of the non-dialysable species varies smoothly from 11 to 3 as free silica in solution ranges from 4 to 35 μg/cm³. Such sols are much less colloidally stable than hydroxyaluminium silicate sols, but mixed Al₂O₃—Fe₂O₃—SiO₂—H₂O sols are almost as stable as iron-free sols up to a Fe : Al ratio of 1.5. Thus migration of Al and Fe as mixed hydroxide sols can account for the almost constant ratio of Al to Fe with depth in oxalate extracts from Bs horizons of podzols.     

Quantification and bioavailability of scyllo-inositol hexakisphosphate in pasture soils

The recent identification of scyllo-inositol hexakisphosphate in alkaline soil extracts by solution ³¹P NMR spectroscopy allowed us to investigate this compound in soils by re-analyzing spectra from two previously published studies. Concentrations of scyllo-inositol hexakisphosphate in 29 temperate pasture soils from England and Wales ranged between 11 and 130 mg P kg⁻¹ soil and accounted for between 4 and 15% of the soil organic phosphorus. The ratio of scyllo-inositol hexakisphosphate to myo-inositol hexakisphosphate ranged between 0.29 and 0.79. In a 10 month pot experiment with six grassland soils from New Zealand, growth of pine seedlings (Pinus radiata D. Don) decreased scyllo-inositol hexakisphosphate concentrations by between 10 and 46%. Growth of ryegrass (Lolium perenne L.) decreased scyllo-inositol hexakisphosphate in three low-nutrient soils by 5-21%, but increased it in three other soils by 11-16%. We conclude that scyllo-inositol hexakisphosphate is an important component of soil organic phosphorus with potential ecological significance.     

Diffusion of NH+4 and NO−3 mineralized from organic N in soil

The mineralization of native soil organic matter and the simultaneous diffusion of zero NH⁺₄ and NO^?₃ to a solution sink of zero N concentration was analysed experimentally and theoretically for a fine sandy loam soil. Experimentally, the NH₄ and NO₃ ions produced in an incubated unsaturated soil column were allowed to diffuse through a sintered glass plate into a stirred solution sink. The distribution of NH⁺₄ and NO^?₃ in the soil column was measured after various incubation times. The rate of ammonification was measured directly during incubation and the rate of nitrification modelled from nitrifier growth kinetics. A Freundlich equation was used to describe the equilibrium between soluble and exchangeable NH⁺₄ in the soil. Terms for the microbial transformation of N and the adsorption-desorption of NH⁺₄ were combined with diffusion equations which were solved numerically using finite difference methods. The model constructed was used to predict the NH⁺₄ and NO^?₃ con-centration distributions in the soil column, and good agreement was obtained between the experimental and predicted concentration profiles. The use of the model for predicting the diffusive flux of mineral N to the outer surfaces of soil peds, where it is vulnerable to leaching, was demonstrated.     

小麦/玉米/大豆和小麦/玉米/甘薯体系中玉米产量及养分吸收的差异

分别在四川2个玉米主产区川中丘区射洪县和川西山区雅安市,采用单因素随机区组设计,通过3年田间试验对比研究了小麦/玉米/大豆和小麦/玉米/甘薯模式下玉米产量、养分吸收积累规律以及与耕层土壤养分的关系。结果表明:两种套作模式经过一年种植后,小麦/玉米/大豆模式下玉米产量均高于小麦/玉米/甘薯模式下的玉米产量,但差异不显著,第二、三年分带轮作后,小麦/玉米/大豆模式下玉米产量显著高于小麦/玉米/甘薯模式下的玉米产量,二年平均分别高出 679.5 kg/hm2和 839.1 kg/hm2,增产9.4%和12.6%,射洪试验点增产作用较雅安试验点显著;分带轮作后两种套作体系玉米氮素吸收积累在拔节前差异不显著,拔节后小麦/玉米/大豆模式下玉米氮素积累量显著高于小麦/玉米/甘薯,磷的吸收积累则相反,从拔节期到开花期,小麦/玉米/大豆模式下玉米磷的吸收积累均显著低于小麦/玉米/甘薯,小麦/玉米/大豆模式下玉米钾素吸收积累量高于小麦/玉米/甘薯;不同作物带耕层土壤养分含量差异达显著水平,大豆带残留的硝态氮、速效氮、速效钾2个试验点平均分别比甘薯带高18.4%、24.1%、6.0%,而铵态氮和速效磷甘薯带较大豆带分别高18.9%和17.1%,两种套作模式中玉米带耕层土壤养分含量差异不显著,经第二、三年分带轮作后,耕层土壤养分含量差异减小,表明分带轮作玉米能较好均衡田间养分。     

Coupled diffusion and oxidation of ferrous iron in soils. II. A model of the diffusion and reaction of O2, Fe2+, H+ and HCO3− in soils and a sensitivity analysis of the model

Kinetic equations are developed for a system in which a column of reduced soil is exposed to oxygen at one end. The equations are combined in a simulation model in which they are solved by finite-difference methods. The model predicts the consequent diffusion of oxygen into the column; the diffusion of ferrous iron towards the oxidation zone; the rate of formation and concentration profile of the ferric hydroxide formed; and the diffusion by acid-base transfer of the acidity produced in the oxidation reaction. A sensitivity analysis of the model, in which runs were made for a wide range of input parameters, showed that for most combinations of parameters, in water-saturated soil, substantial amounts of iron are transferred towards the air-exposed surface, leading to a well-defined zone of ferric hydroxide accumulation. The profile of total iron in this zone is often banded. The pH in the zone falls by at least two units. A small amount of air-filled pore space increases the depth of the oxidation front dramatically. The model indicates that coupled iron oxidation and diffusion reactions, which are very widespread in natural soils, may be understood quantitatively.     

3 种挺水植物吸收水体NH4+、NO3-、H2PO4- 的动力学特征比较

本文用动力学试验研究了具有景观价值的3 种挺水植物—— 水生美人蕉(Canna generalis)、细叶莎草(Cyperus papyrus)、紫芋(Colocasia tonoimo)对H₂PO₄^-、NH₄⁺、NO₃^- 的吸收特征及差异。试验结果表明: 3 种挺水植物吸收H₂PO₄^- 时, 美人蕉的吸收速率最快, 且在较低离子浓度条件下也可以吸收该离子, 说明其具有嗜磷特性, 能够适应广范围浓度H₂PO₄^- 环境; 吸收NO₃^- 时, 细叶莎草的速率最快, 但对低浓度NO₃^- 环境的适应能力较差, 美人蕉吸收NO₃^- 的特性与细叶莎草刚好相反; 吸收NH₄⁺ 时, 细叶莎草的吸收速率最快, 且在低浓度NH₄⁺ 环境下仍能吸收该离子, 而美人蕉的吸收速率最慢, 但能在低浓度NH₄⁺ 环境下吸收该离子。说明不同植物对养分的吸收特性存在较大差异, 各自的污染水体修复适用范围也不同。美人蕉可用于各种浓度H₂PO₄^- 污染的水体修复; 而NO₃^- 污染严重的水体最适宜用细叶莎草作先锋植物, 修复到一定程度后再种植美人蕉来维持水质; 细叶莎草在各种浓度NH₄⁺ 污染的水体中均适用, NH₄⁺ 污染较轻的水体也可用美人蕉修复。     

LC/UV/ESI-MS analysis of isoflavones in Edamame and Tofu soybeans

High-performance liquid chromatography coupled with ultraviolet and electrospray ionization mass spectrometry (HPLC/UV/ESI-MSD) was applied to the study of isoflavones in both Edamame and Tofu soy varieties, from which the immature fresh soybeans or the mature soybean seeds are consumed, respectively. Positive atmospheric pressure interface (API) MS and MS/MS were used to provide molecular mass information and led to the identification of a total 16 isoflavones, including three aglycones, three glycosides, two glycoside acetates, and eight glycoside malonates. The major isoflavones in soybean seeds were daidzein and genistein glycoside and their malonate conjugates. Trace levels of daidzein and genistein acetyl glycosides were found only in the mature dry soybean seeds. To facilitate quantitative analysis, acid hydrolysis during extraction of soy samples was selected to convert the various phytoestrogen conjugates into their respective isoflavone aglycones, allowing accurate quantitation of total phytoestrogens as aglycones. On the basis of HPLC combined with UV and MS detection, all three targeted soy isoflavone aglycones, daidzein, genistein and glycitein in hydrolyzed extracts were successfully quantified within 25 min with formononetin used as the internal standard. The standard curves of UV detection were fitted in the range of 14.16-29000 ng/mL for daidzein, 15.38-31500 ng/mL for genistein, and 11.72-24000 ng/mL for glycitein. For MS detection, the standard curves were established in the range of 3.54-1812.5 ng/mL for daidzein, 3.85-1968.75 ng/mL for genistein, and 2.93-1500 ng/mL for glycitein. Good linearities (r(2) > 0.999 for UV and r(2) > 0.99 for MS) for standard curves were achieved for each isoflavone. The accuracy and precision (RSD) were within 10% for UV detection and 15% for MS detection (n = 10). Using this method, the phytoestrogen levels of total isoflavone aglycones from 30 soybean seed varieties were then evaluated for confirmation of the technique. Total isoflavones ranged across the varieties from 0.02 to 0.12% in the Edamame varieties, which are harvested while the seeds are still immature, and from 0.16 to 0.25% in Tofu varieties, harvested when the seeds are physiologically mature. While the literature has focused on the isoflavone content of soy products and processing soy, this report provides a reliable analytical technique for screening of authenticated fresh immature Edamame soybeans and Tofu soybeans.     

伴矿景天和鹅掌柴间作系统中根系相互作用对植物生长和镉锌吸收的影响

为明确不同物种根系间的相互作用对植物生长和重金属元素吸收的影响,以Cd、Zn超积累植物伴矿景天与花卉植物鹅掌柴为材料,研究二者根系相互作用及对植物生长和Cd、Zn的影响。结果发现,二者根系具有相互抑制生长的作用。单作条件下伴矿景天的Cd、Zn吸收量最高,分别达0.812、19.6 mg/盆;较单作相比,无分隔间作条件下伴矿景天对土壤Cd、Zn吸收降低分别达30.0%和30.6%。两种植物根系改变了土壤养分性质,对土壤钾和磷的利用分别具有竞争和互补作用,但其有效态含量并未降低到亏缺水平,养分竞争可能不是两种植物根系相互作用的主要因素。水培试验表明鹅掌柴根系分泌物对伴矿景天的生长和Cd吸收具有抑制作用。     

Survey of residual nitrite and nitrate in conventional and organic/natural/uncured/indirectly cured meats available at retail in the United States

A survey of residual nitrite (NO(2)(-)) and nitrate (NO(3)(-)) in cured meats available at retail was conducted to verify concentrations in conventional (C) products and establish a baseline for organic/natural/uncured/indirectly cured (ONC) products. In this study, 470 cured meat products representing six major categories were taken from retail outlets in five major metropolitan cities across the United States. Random samples representing both C and ONC type products were analyzed for NO(2)(-) and NO(3)(-) content (ppm) using an ENO-20 high-performance liquid chromatography system equipped with a reverse phase column. Generally, there were no differences in NO(2)(-) concentrations between C and ONC meat categories, but a few ONC products surveyed in certain cities were lower in NO(3)(-) content. Pairwise comparisons between cities indicated that NO(2)(-) and NO(3)(-) contents of all C type products were not appreciably different, and the same was true for most ONC products. Numerical NO(2)(-) values were less variable than NO(3)(-) concentrations within each meat product category. NO(2)(-) concentrations were similar to those previously reported by Cassens ( Cassens , R. G. Residual nitrite in cured meat . Food Technol. 1997a , 51 , 53 - 55 ) in 1997. Residual NO(2)(-) and NO(3)(-) values in this study were numerically lower than those reported by NAS ( National Academy of Sciences . The Health Effects of Nitrate, Nitrite, and N-Nitroso Compounds ; National Academy Press : Washington, DC , 1981 ) in 1981. Data from this survey provide a benchmark of NO(2)(-) and NO(3)(-) concentrations for ONC products available at retail.     

Assessment of N2O, NOx and NH3 emissions from a typical rural catchment in Eastern China

To evaluate the atmospheric load of reactive gaseous nitrogen in the fast-developing Eastern China region, we compiled inventories of nitrous oxide (N₂O), nitrogen oxide (NO_x) and ammonia (NH₃) emissions from a typical rural catchment in Jiangsu province, China, situated at the lower reach of the Yangtze River. We considered emissions from synthetic N fertilizer, human and livestock excreta, decomposition of crop residue returned to cropland and residue burning, soil background and household energy consumption. The results showed that, for the 45.5 km² catchment, the annual reactive gaseous emission was 279 ton N, of which 7% was N₂O, 16% was NO_x and 77% was NH₃. Synthetic N fertilizer application was the dominant source of N₂O and NH₃ emissions and crop residue burning was the dominant source of NO_x emission. Sixty-seven percent of the total reactive gaseous N was emitted from croplands, but on a per unit area basis, NO_x and NH₃ emissions in residential areas were higher than in croplands, probably as a result of household crop residue burning and extensive human and livestock excreta management systems. Emission per capita was estimated to be 18.2 kg N year⁻¹ in the rural catchment, and emission per unit area was 56.9 kg N ha⁻¹year⁻¹ for NH₃ + NO_x, which supports the observed high atmospheric N deposition in the catchment. Apparently, efficient use of N fertilizer and biological utilization of crop straw are important measures to reduce reactive gases emissions in this rural catchment.     

13C and 15N natural abundances of urban soils and herbaceous vegetation in Karlsruhe, Germany

We undertook what we believe to be a unique survey of the natural abundances of ¹³C and ¹⁵N in urban soils and plants in Karlsruhe (Germany), a European city of average size. We found broad patterns of these abundances in both soils and plants, which reflected geology and land use. In contrast with studies on smaller areas (showing the direct effect of human activities), our study first determined the extent to which the abundances correlated with land use or underlying geology and then assessed how we could further test such relationships. The spatial pattern of δ¹³C in surface soil correlated with that of the underlying parent material; construction activities superimposed a secondary signal. Maize cultivation was a source of less negative soil δ¹³C, whereas the C₃ vegetation is a source of more negative soil δ¹³C. There was a footprint of less negative plant δ¹³C in the industrial and port areas; plant δ¹³C downwind of the city was less negative than upwind, which might relate to atmospheric pollution from the port area or to differences in soil properties. There was no significant effect of wind direction or geology on soil or plant δ¹⁵N, which was correlated mainly with land use. The largest soil δ¹⁵N was under agriculture and the smallest under woodland. The abundance of ¹⁵N in inner-urban soil and plants was intermediate between those of agriculture and forests. This study represents a major advance in the use of stable isotope geochemistry in understanding urban environments.     

Improved zinc tolerance in Eucalyptus globulus inoculated with Glomus deserticola and Trametes versicolor or Coriolopsis rigida

The potential of interactions between saprophytic and arbuscular mycorrhizal (AM) fungi to improve Eucalyptus globulus grown in soil contaminated with Zn were investigated. The presence of 100 mg kg ⁻¹ Zn decreased the shoot and root dry weight of E. globulus colonized with Glomus deserticola less than in plants not colonized with AM. Zn also decreased the extent of root length colonization by AM and the AM fungus metabolic activity, measured as succinate dehydrogenase (SDH) activity of the fungal mycelium inside the E. globulus root. The saprophytic fungi Trametes versicolor and Coriolopsis rigida increased the shoot dry weight and the tolerance of E. globulus to Zn when these plants were AM-colonized. Both saprophytic fungi increased the percentage of AM root length colonization and elevated G. deserticola SDH activity in the presence of all Zn concentrations applied to the soil. In the presence of 500 and 1000 mg kg⁻¹ Zn, there were higher metal concentrations in roots and shoots of AM than in non-AM plants; furthermore, both saprophytic fungi increased Zn uptake by E. globulus colonized by G. deserticola. The higher root to shoot metal ratio observed in mycorrhizal E. globulus plants indicates that G. deserticola enhanced Zn uptake and accumulation in the root system, playing a filtering/sequestering role in the presence of Zn. However, saprophytic fungi did not increase the root to shoot Zn ratio in mycorrhizal E. globulus plants. The effect of the saprophytic fungi on the tolerance and the accumulation of Zn in E. globulus was mediated by its effect on the colonization and metabolic activity of the AM fungi.     

Pathways and dynamics of NO3 and NH4 applied in a mountain Picea abies forest and in a nearby meadow in central Switzerland

To evaluate the pathways and dynamics of inorganic nitrogen (N) deposition in previously N-limited ecosystems, field additions of ¹⁵N tracers were conducted in two mountain ecosystems, a forest dominated by Norway spruce (Picea abies) and a nearby meadow, at the Alptal research site in central Switzerland. This site is moderately impacted by N from agricultural and combustion sources, with a bulk atmospheric deposition of 12 kg N ha⁻¹ y⁻¹ equally divided between NH₄⁺ and NO₃⁻. Pulses of ¹⁵NH₄⁺ and ¹⁵NO₃⁻ were applied separately as tracers on plots of 2.25 m². Several ecosystem pools were sampled at short to longer-term intervals (from a few hours to 1 year), above and belowground biomass (excluding trees), litter layer, soil LF horizon (approx. 5-0 cm), A horizon (approx. 0-5 cm) and gleyic B horizon (5-20 cm). Furthermore, extractable inorganic N, and microbial N pools were analysed in the LF and A horizons. Tracer recovery patterns were quite similar in both ecosystems, with most of the tracer retained in the soil pool. At the short-term (up to 1 week), up to 16% of both tracers remained extractable or entered the microbial biomass. However, up to 30% of the added ¹⁵NO₃⁻ was immobilised just after 1 h, and probably chemically bound to soil organic matter. 16% of the NH₄⁺ tracer was also immobilised within hours, but it is not clear how much was bound to soil organic matter or fixed between layers of illite-type clay. While the extractable and microbial pools lost ¹⁵N over time, a long-term increase in ¹⁵N was measured in the roots. Otherwise, differences in recovery a few hours after labelling and 1 year later were surprisingly small. Overall, more NO₃⁻ tracer than NH₄⁺ tracer was recovered in the soil. This was due to a strong aboveground uptake of the deposited NH₄⁺ by the ground vegetation, especially by mosses.     

Phytosequestration of Carbon in Miscanthus × giganteus and Pinus sylvestris L. in Degraded Zinc Smelter and Post-Mining Soils

正Dear Editor,Pinus sylvestris L.is one of the most popular and predominant tree species in Central Europe and Scandinavia.Its cultivation depends on atmospheric conditions,soil fertility,use of fertilizers,and individual characteristics of the trees.Pinus sylvestris L.wood,roots,and needles are used for energy production.Pi-     

Temporal shifts in diversity and quantity of nirS and nirK in a rice paddy field soil

Denitrification is an important part of the nitrogen cycle in the environment, and diverse bacteria, archaea, and fungi are known to have denitrifying ability. Rice paddy field soils have been known to have strong denitrifying activity, but the microbes responsible for denitrification in rice paddy field soils are not well known. Present study analyzed the diversity and quantity of the nitrite reductase genes (nirS and nirK) in a rice paddy field soil, sampled four times in one rice-growing season. Clone library analyses suggested that the denitrifier community composition varied over sampling time. Although many clones were distantly related to the known NirS or NirK, some clones were related to the NirS from Burkholderiales and Rhodocyclales bacteria, and some were related to the NirK from Rhizobiales bacteria. These denitrifiers may play an important role in denitrification in the rice paddy field soil. The quantitative PCR results showed that nirK was more abundant than nirS in all soil samples, but the nirK/nirS ratio decreased after water logging. These results suggest that both diversity and quantity changed over time in the rice paddy field soil, in response to the soil condition.     

鱼源嗜水气单胞菌aopB-/aopD-/aroA-缺失株的构建及鉴定

嗜水气单胞菌(Aeromonas hydrophila)能引起多种鱼类暴发性出血性败血症,为研制更加安全的嗜水气单胞菌口服活疫苗,构建了鱼源嗜水气单胞菌aopB-/aopD-/aroA-缺失株。首先构建含缺失369 bp的aopB/aopD基因(编码嗜水气单胞菌外膜蛋白B、D)与蔗糖敏感基因(sacB)的重组自杀性质粒pREaopB/aopD,与嗜水气单胞菌Ah2056接合转移,应用二步法筛选aopB-/aopD-缺失株,PCR证实aopB/aopD基因的缺失突变。在此基础上,构建另一个含缺失1 290 bp的aroA基因(编码5-酸烯醇式丙酮酸莽草酸-3-磷酸合酶)与庆大霉素抗性片段（aacC1片段）的重组自杀性质粒pSUParoA,与aopB-/aopD-缺失株接合转移,利用庆大霉素抗性筛选aopB-/aopD-/aroA-缺失株,用PCR证实aroA基因的缺失突变。进一步对aopB-/aopD--/aroA-缺失株进行生长特性、对鱼的毒力等生物学特性鉴定。结果表明,aopB-/aopD-/aroA-缺失株构建成功,且该缺失株为毒力丧失、营养缺陷株。