多种有机酸对土壤中碳酸镉的活化效应

采用振荡活化方法,探究44种有机酸对碳酸镉的活化差异及其机理,评价活化能力较强的5种有机酸对低浓度Cd污灌菜园土的活化效应。结果表明：低分子有机酸、酚酸及氨基酸对碳酸镉的活化能力存在明显差异;低分子有机酸活化能力总体较强,其中草酸、柠檬酸活化率达7.48%、7.06%。等摩尔浓度有机酸活化效果计算表明：柠檬酸的活化效果最大,活化量为22.73 mg·L-1,其次是苹果酸和顺乌头酸,分别为14.55和12.75 mg·L-1,酚酸的活化效果不明显,氨基酸中除天冬氨酸、组氨酸和谷氨酸活化效果较强,其余无明显效果。研究表明在等摩尔浓度时,柠檬酸活化碳酸镉主要机制为官能团的螯合作用,而草酸主要为酸溶作用;活化碳酸镉能力较强的柠檬酸对污灌菜园土低浓度Cd的活化最强,对镉的活化量达到食品安全风险水平。     

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.     

Long-term tillage effects on soil metolachlor sorption and desorption behavior

Sorption and desorption are two important processes that influence the amount of pesticides retained by soils. However, the detailed sorption mechanisms as influenced by soil tillage management are unclear. This study examined the sorption and desorption characteristics of metolachlor [2-chloro-N-(2-ethyl-6-methyphenyl)-N-(2-methoxy-1-methylethyl)-acetamide] using the soil samples collected from the long-term conservation tillage (CnT) and conventional tillage (CT) research plots established in 1979 in Darlinton, SC. Humic acid (HA) and humin were extracted from the soils and used in the sorption experiments along with the whole soil samples. The sorption experiments were conducted using a batch-equilibration method. Three sequential desorption rinses were carried out following the sorption experiments. By comparing metolachlor sorption and desorption results we observed hysteresis for all soil samples and their organic matter fractions. Sorption nonlinearity (N) and hysteresis were dependent on the structure and composition of soil organic matter (SOM), e.g., Freundlich isotherm exponents (N) of HA and humin from CnT were higher than those of CT treatment, which may be related to high aromaticity of SOM fractions in CT treatment. Sorption capacity (K'f) was positively correlated with soil organic carbon (SOC) content. These results show that long-term tillage management can greatly affect metolachlor sorption and desorption behavior probably by qualitative differences in the structural characteristics of the humic substances.     

Contrasting effects of silicates on cadmium uptake by three dicotyledonous crops grown in contaminated soil

The effects of several silicates (talcum powder (TP), calcium silicate (CS), sodium silicate (SS), and potassium silicate (PS)), in comparison with other amendments (quicklime (QL) and potassium dihydrogen phosphate (PDP)) on cadmium (Cd) uptake by three dicotyledonous crops (Amaranthus hypochondriacus L. Cv. ‘K112’, Amaranthus tricolor L., and Brassica oleracea var. albiflora Kuntze) were investigated in Cd–contaminated soil. The effects of both application methods of amendments (singly and combined) and timing of application were also evaluated. Sodium silicate was the most effective in reducing crop Cd uptake and translocation, which was diminished by 51 % in roots, 53 % in stems, and 72 % in leaves on average. Application of CS amendment showed greater efficiency than PDP amendment in decreasing Cd uptake by crops and resulted in increased biomass. Potassium silicate only slightly decreased shoot Cd concentration. Combination of PDP and SS was able to overcome the inhibitory effect of SS on crop yield while decreasing Cd concentrations in roots, stems and leaves of the tested crops by average rates of 52, 65, and 68 % respectively. Applications of SS and PS significantly reduced the root-to-shoot Cd transfer factor. We found that Si accumulation in crops was not associated with lower Cd concentration, indicating that Si in crops may play a major role in alleviating metal stress rather than inhibiting crop Cd accumulation. We suggested that the inhibitive effect of silicates on crops Cd uptake was majorly attributed to the properties of the silicates, those were their specific effects on soil pH and cations, which increased Cd adsorption by soil and suppressed Cd uptake from soil solution by increasing the relative dissolved concentrations of competing cations.     

Long-term effects of fertilization on the forms and availability of soil phosphorus in rice paddy

The changes in total P accumulation and P compounds with time in the plough layer in a paddy soil in southern Korea were investigated in relation to the continuous application of chemical fertilizers (NPK), straw based compost (Compost), combination these two (NPK+Compost) for 31 years. Continuous fertilization increased the total and inorganic P contents in plough layers. In NPK, inorganic P fraction did not change with time, but organic P content increased significantly. Long-term application of chemical fertilizer together with compost accelerated the decrease in the organic P fraction, presumably due to promoting microbial activity in the plow layer, and then increased significantly inorganic P fraction. Compost application decreased the residual P and Fe-P fractions and then increased inorganic P fraction, in spite of continuous compost application. Increase in total, inorganic and extractable P with time may be closely related to the increase in the availability of accumulated P for rice growth.     

Long-term effects of amendment with liquid swine manure on proton binding behavior of soil humic substances

The acid-base properties of humic acids (HAs) and fulvic acids (FAs) isolated from liquid swine manure (LSM), soils amended with either 90 or 150 m(3)ha(-1)year(-1) of LSM for 7 years, and the corresponding unamended control soil were investigated by a current potentiometric titration method. The non-ideal competitive adsorption (NICA)-Donnan model for proton binding by two classes of binding sites (i.e., carboxylic- and phenolic-type groups) was fit to titration data, and a set of fitting parameters was obtained for each HA and FA sample. The NICA-Donnan model was shown to describe with a great degree of accuracy the behavior of experimental titration datasets, and highlighted important differences in the acid-base properties of the HAs and FAs examined. When compared to the unamended soil HA and FA, LSM-HA and LSM-FA, had smaller acidic functional group contents, larger proton binding affinities of both carboxylic- and phenolic-type groups, smaller heterogeneity of carboxylic-type groups, and smaller, in the case of HA, or similar, in the case of FA, heterogeneity of phenolic-type groups. Amendment with LSM caused a decrease of acidic functional group contents and a slight increase of proton binding affinities of carboxylic- and phenolic-type groups of soil HAs and FAs. Further, LSM application induced a decrease of the heterogeneity of carboxylic-type groups, whereas appeared not to affect substantially the heterogeneity of phenolic-type groups of LSM-amended soil HAs and FAs. These effects were more evident for HAs than for FAs and tended to slightly increase with increasing LSM amendment rate.     

Contrasting behaviour of cadmium and zinc in a soil-plant-arthropod system

This study investigates the transfer of Cd and Zn from a soil amended with sewage sludge at rates up to 100 t ha(-1) through a multi-trophic system consisting of barley, the aphid Sitobion avenae and the larvae of the lacewing Chrysoperla carnae. Results show marked differences in the transfer of the two metals. Cadmium was freely accumulated in barley roots, but accumulation in the shoot was restricted to a concentration of around 0.22 mg kg(-1) (dry weight). This limited the transfer of Cd to higher trophic levels and resulted in no significant accumulation of Cd in S. avenae or in C. carnae. Zinc transfer in the system was largely unrestricted, resulting in significant accumulation in roots and shoots, in S. avenae and in C. carnae. Cadmium biomagnification occurred in lacewing pupae, with concentrations up to 3.6 times greater than in aphids. S. avenae biomagnified Zn by a factor of ca. 2.5 at low sludge amendment rates, but biomagnification decreased to a factor of 1.4 at the highest amendment rate. Biomagnification of Zn did not occur in C. carnae, but concentrations were up to 3.5 time higher than in soil. Results are discussed in light of the mechanisms regulating transfer of the two metals in the system.     

Long-term effects of clear-cutting and selective cutting on soil methane fluxes in a temperate spruce forest in southern Germany

Based on multi-year measurements of CH₄ exchange in sub-daily resolution we show that clear-cutting of a forest in Southern Germany increased soil temperature and moisture and decreased CH₄ uptake. CH₄ uptake in the first year after clear-cutting (−4.5 ± 0.2 μg C m⁻² h⁻¹) was three times lower than during the pre-harvest period (−14.2 ± 1.3 μg C m⁻² h⁻¹). In contrast, selective cutting did not significantly reduce CH₄ uptake. Annual mean uptake rates were −1.18 kg C ha⁻¹ yr⁻¹ (spruce control), −1.16 kg C ha⁻¹ yr⁻¹ (selective cut site) and −0.44 kg C ha⁻¹ yr⁻¹ (clear-cut site), respectively. Substantial seasonal and inter-annual variations in CH₄ fluxes were observed as a result of significant variability of weather conditions, demonstrating the need for long-term measurements. Our findings imply that a stepwise selective cutting instead of clear-cutting may contribute to mitigating global warming by maintaining a high CH₄ uptake capacity of the soil.     

鼠李糖脂协助下的土壤中镉电动修复

实验研究了重金属Cd在生物表面活性剂鼠李糖脂协助下的电动修复过程,通过不同方式、不同浓度、不同酸碱度的鼠李糖脂溶液的添加与空白处理对比,探讨了鼠李糖脂协助下电动修复过程中的Cd在土壤介质中的迁移转化和机理,分析了鼠李糖脂溶液作为电动修复添加剂的可行性。结果表明,中等浓度酸性的鼠李糖脂溶液(pH=4.78,浓度为0.5、1和2 g/L)能对土壤中的重金属Cd进行有效的富集,富集量均在初始值的4倍以上,且其可交换态比重均大于42.07%,非常有利于土壤进行二次修复。此外,以pH=4.78,浓度为0.5 g/L的鼠李糖脂溶液作为预处理剂的Ex-08中的重金属Cd并未出现富集现象,但其对重金属的Cd的总去除效率达到了49.27%。表明利用鼠李糖脂溶液作为电动修复添加剂进行土壤重金属修复是可行的。     

Ecotoxicological effects of cadmium on three ornamental plants

Ecotoxicological effects of cadmium (Cd) on three ornamental plants African marigold (Tagetes erecta), scarlet sage (Salvia splendens) and sweet hibiscus (Abelmoschus manihot) were investigated. Seeds of these plants were exposed to five different concentrations of Cd (0-50 mgl(-1)). Ecotoxicological indexes based on inhibition rate (IC) of seed germination, root and shoot elongation, biomass (fresh weight and dry weight), as well as IC50 (Cd concentration when 50% plants show inhibition) and tolerance indexes (the ratio of maximum root length in an experimental group to that in a control group) were determined. The results indicated that Cd had little effects (p>0.05) on seed germination of the three plants and shoot elongation of scarlet sage (S. splendens). Cadmium had significant (p<0.05) inhibitory effects on root elongation of the three plants and shoot elongation of African marigold (T. erecta). The fresh weight biomass of scarlet sage (S. splendens) was most sensitive to Cd, while that of sweet hibiscus (A. manihot) was least sensitive. On a dry weight basis, African marigold (T. erecta) was the least sensitive, and scarlet sage (S. splendens) was the most sensitive to Cd. Based on IC50 of seed germination, sweet hibiscus (A. manihot) was the most insensitive plant with an IC50 value as high as 428.0 gl(-1). According to Cd-tolerance indexes under the same Cd concentration, sweet hibiscus (A. manihot) was the most tolerant plant whereas scarlet sage (S. splendens) was the most sensitive one.     

硫化钠对土壤中铅镉的固定效果简

研究了硫化钠用于固定土壤中铅镉的可行性,考察了硫化钠用量及土壤pH、有机质对固定过程中土壤铅、镉赋存形态及固定效果的影响。结果表明,添加硫化钠可改变土壤中铅镉的形态分布,明显降低可交换态铅镉的含量。条件适当时,铅镉可交换态下降值分别为63%和73%。硫化钠在固定铅的过程中,固定效率对土壤pH、有机质含量的变化较为敏感,在有机质含量较低或酸性土壤中,硫化钠对铅固定效率较高;相对于铅,有机质含量和pH变化对镉的固定效率影响不是很大。     

添加天然沸石和石灰对土壤镉形态转化的影响

采用土壤培养实验,研究镉污染土壤中添加沸石、石灰及两者配施对土壤pH值和土壤镉形态变化的影响。结果表明,土壤pH值随沸石用量的增加而增加,随培养时间呈现先增加后下降并逐渐趋于稳定的趋势,但均高于对照。高剂量石灰的处理对土壤pH的影响最大,与对照相比土壤pH提高了3.33个单位。在土壤5~50 d培养过程中,石灰处理的土壤交换态镉含量呈现先逐渐降低而后略有升高的趋势,其余处理均呈下降趋势。培养50 d后,高剂量的沸石、石灰及高剂量沸石与石灰配施处理的土壤交换态镉含量从5 d时的67.54、61.95和55.56 mg/kg降低至54.65、49.93和45.96mg/kg。相关分析表明,不同培养时期交换态镉含量与土壤pH值呈负相关关系。在10个处理中,L2Z3(石灰2 g/kg土和沸石60 g/kg土)组合处理效果最好,使土壤交换态镉含量下降了34.68%,碳酸盐结合态镉含量上升了4.30%,铁锰氧化结合态镉含量上升了16.97%,有机结合态镉含量上升了1.31%,残渣态镉含量上升了12.11%。     

Regional distribution of cadmium minerals and risk assessment for potential cadmium pollution of soil in China

系统地分析和评价了中国镉矿的区域分布及长期采选冶活动所带来的土壤镉污染风险.研究结果表明,截至2005年底,中国累计探明镉资源储量约为719.47kt,保有镉资源储量约为587.37 kt,且多与铅矿、锌矿等以共、伴生形式存在.中国镉矿主要分布在中部、西南部及华东地区,这些地区的镉资源探明储量占中国累计探明总储量的88.0％,保有储量占中国总保有储量的87.1％.据统计,中国镉采出量约为136.10 kt,主要集中在西南地区,其镉采出量占中国总采出量的59.4％.镉污染事件主要发生在镉矿相对丰富及采选冶活动较密集的云南、广东、湖南、贵州等地区,大部分矿冶区及周边土壤呈现重度镉污染,农作物中含镉量超出《食品中污染物限量》(GB2762-2005)中限值.     

电动修复技术对土壤中镉迁移的影响

以镉含量为200 mg·kg-1的模拟污染土壤为研究对象,使用电动修复技术对土壤中的镉进行去除。实验研究了不同修复电压下电流密度、电解液pH值、土壤中镉含量的变化,并重点研究了修复电压对土壤中镉迁移的影响规律。实验结果表明,通电电压越大,电场强度越强,镉的迁移量越大,电动修复效率越高,当修复电压为50 V时,阴极区域附近镉的迁移量与修复电压为5 V时相同位置镉的迁移量相比可以提高30%,实验结果为重金属污染土壤电动修复过程中镉的迁移量化研究提供了参考。     

有机酸对成都平原镉污染土壤的淋洗效果

以成都平原某化工厂附近受Cd污染的2种土壤为对象,采用振荡淋洗技术,研究了有机酸在不同浓度、固液比、振荡时间和复合淋洗条件下对重金属Cd的去除效果。实验结果表明：柠檬酸和酒石酸对Cd含量为22.78 mg·kg-1的SLT-01土壤具有更好的去除效果,分别达到73%和62%,而乙酸和草酸的去除能力较低;随着固液比的降低,有机酸对Cd的去除率逐步提高;随着时间的增加,Cd的去除率波动增加;柠檬酸和酒石酸复合淋洗并没有提高Cd的去除率;振荡淋洗前后土壤结构未发生明显变化。综合考虑土壤中Cd的去除效果和成本,选择柠檬酸作为最佳淋洗剂;最佳实验条件：溶液浓度为0.10 mol·L-1,固液比为1∶20,淋洗时间为8 h。     

土壤中Pb、Cd的稳定化修复技术研究进展

在众多重金属修复技术当中,稳定化技术具有花费少、环境损失小等诸多优势。综述了国内外土壤中Pb、Cd稳定化修复的研究进展;分析了稳定剂的作用机制、土壤中Pb、Cd的赋存形态;探讨了土壤中Pb、Cd稳定化修复的主要影响因素。最后,还提出了稳定化修复技术在土壤中Pb、Cd污染治理应用中尚存在的问题。     

Potential contribution of arbuscular mycorrhiza to cadmium immobilisation in soil

The contribution of arbuscular mycorrhiza (AM) to immobilisation of Cd in substrate was studied in two experiments. In the first experiment, substrates prepared by cultivating tobacco, either non-mycorrhizal or inoculated with the AM fungus Glomus intraradices were enriched with a range of Cd concentrations, and Cd toxicity in the substrates was assessed using root growth tests with lettuce as a test plant. The tests revealed lower Cd toxicity in the mycorrhizal than in the non-mycorrhizal substrate, and the difference increased with increasing total Cd concentration in the substrates. In the second experiment, extraradical mycelium (ERM) of G. intraradices exposed in vivo to Cd was collected and analysed on Cd concentration. The ERM accumulated 10–20 times more Cd per unit of biomass than tobacco roots. While Cd concentrations were lower in the biomass of mycorrhizal plants than of non-mycorrhizal plants, Cd immobilisation by ERM did not affect the total Cd content in mycorrhizal tobacco.

It is concluded that mycorrhiza may decrease Cd toxicity to plants by enhancing Cd immobilisation in soil. The results therefore suggest a potential role of AM symbiosis in the phytostabilisation of contaminated soils, where high Cd availability inhibits plant growth.     

Silicon-mediated enhancement of cadmium tolerance in maize (Zea mays L.) grown in cadmium contaminated soil

Pot experiments were performed to study the alleviative effects of exogenous silicon (Si) on cadmium (Cd) phytotoxicity in maize grown in an acid soil experimentally contaminated with Cd. Five treatments were investigated in the first trial consisting of a control (neither Cd nor Si added), Cd added at 20 or 40 mg kg(-1) Cd without or with Si added at 400 mg kg(-1) Si. A following-up trial was conducted with almost the same treatments as in the first trial except that Si was incorporated at 50 mg kg(-1) Si. The results showed that Cd treatment significantly decreased shoot and root dry weight, while addition of Si at both levels significantly enhanced biomass. Addition of Si at 400 mg kg(-1) Si significantly increased soil pH but decreased soil Cd availability, thus reducing Cd concentration in the shoots and roots and total Cd in the shoots. Moreover, more Cd was found to be in the form of specific adsorbed or Fe-Mn oxides-bound fraction in the Si-amended soil. In contrast, soil pH, available Cd and Cd forms were unaffected by addition of Si at 50 mg kg(-1) Si, but shoot Cd concentration in the Si-amended Cd treatments significantly decreased at both Cd levels used compared to the non-Si-amended Cd treatments. Total Cd in the shoots and roots was considerably and significantly higher in the Si-amended Cd treatments than in the non-Si-amended Cd treatments. The xylem sap significantly increased but Cd concentration in the xylem sap significantly decreased in the Si-amended Cd treatments compared with the non-Si-amended Cd treatments irrespective of Cd and Si levels used. The results suggest that Si-enhanced tolerance to Cd can be attributed not only to Cd immobilization caused by silicate-induced pH rise in the soils but also to Si-mediated detoxification of Cd in the plants.     

Long-term effect of sewage sludge application on soil humic acids

Sewage sludges are used in agriculture because they act as a fertilizer. Long-term studies are needed to evaluate the effect of sewage sludge on soil properties by paying particular attention to the soil organic matter. Soil plots were amended for 10 years with 1Mg dry matter ha(-1)year(-1) of sewage sludge. Chemical parameters such as total organic carbon (TOC), N, C/N ratio and CEC were determined when this period ended. Moreover, TOC was fractionated into humified and non-humified fractions. Humic acids (HA) were isolated and studied by elemental analysis, DRIFT, (1)H NMR and CPMAS 13C NMR spectroscopies. At the end of the tests, compared to the control soil, the sludge-amended soil did not exhibit change in total organic C and related humified fractions. However, the HA composition of the soil treated with sludge had developed an HA composition closer to that of the HA-sludge as a result of the enrichment of recalcitrant fractions contained in the sludge.