矿物基蚯蚓粪表面特征及其对土壤Cd钝化能力的研究

针对农田土壤镉（Cd）活性高的问题,以寻求具有良好重金属钝化特性的原位修复材料为目标,该研究以铁粉、磷矿粉和牛粪混合蚯蚓堆肥所制备的矿物基蚯蚓粪为研究对象,利用系列结构表征手段对其进行基本性质表征,并进一步分析矿物基蚯蚓粪施加下土壤对Cd吸附、有效性和赋存形态的影响,最终筛选出具有良好Cd钝化效果的矿物基蚯蚓粪。结果表明,铁粉及磷矿粉的添加使矿物基蚯蚓粪中的pH值、C/N、有机质含量有所降低,但总养分含量显著增加（P＜0.05）。全自动比表面积及孔隙度、扫描电镜分析和X射线能谱分析结果表明,矿物质的添加增大了蚯蚓粪比表面积和孔容,改变了蚯蚓粪中矿物元素的占比。傅立叶变换红外光谱分析表明,矿物基蚯蚓粪中醇或羧酸类、芳香类以及多糖类物质增多,脂类和碳水化合物减少。X射线衍射分析表明,添加铁粉及磷矿粉制备出来的矿物基蚯蚓粪增加了磷酸盐、纳米零价铁等矿物组分。土壤培养和吸附解吸试验表明,施加矿物基蚯蚓粪显著提升了土壤对Cd的吸附强度,降低了对Cd的解吸率,其中以牛粪+20%铁粉+20%磷矿粉（VCFe+P）进行蚯蚓堆肥所获得的矿物基蚯蚓粪处理的土壤对Cd的吸附效果最佳,较施加纯蚯蚓粪的土壤吸附容量提升137.66%,解吸率降低7.34%～12.76%;该处理的土壤Cd钝化率高达50.02%,Tessier 形态分析结果表明,VCFe+P矿物基蚯蚓粪使交换态Cd向铁锰氧化态Cd和残渣态转化。综上,20%铁粉+20%磷矿粉+牛粪混合蚯蚓堆肥所制备的矿物基蚯蚓粪具有良好的Cd吸附表面特征和高效的Cd钝化能力,在土壤Cd污染修复方面具有较大的应用前景。     

应用XAFS研究草酸根和胡敏酸对As(V)在红壤中吸附的影响

结合吸附实验和X光吸收精细结构光谱(XAFS)分析,研究了草酸根和胡敏酸对As(V)在红壤中吸附的影响,分析了As(V)在红壤中的化学形态和微观结构以及草酸根、胡敏酸的影响特征。结果表明,当pH6.0时,红壤主要是通过基团交换反应吸附As(V),草酸根和胡敏酸可以通过竞争吸附位点抑制红壤中As(V)的吸附,其抑制作用随浓度增大而增强。XAFS光谱学数据表明,红壤中吸附的砷以+5价态存在,主要与铁铝矿物形成以约0.317 nm As-Al和0.328 nm As-Fe原子间距为特征的双齿双核结构的内层复合物,复合物结构类型不受砷浓度和草酸根、胡敏酸的影响。     

矿物对溶解性有机质及其不同组分的吸附作用

溶解性有机质(Dissolved Organic Matter,DOM)在土壤矿物表面的吸附控制着其在土壤中的迁移,会影响土壤/矿物对重金属、有机污染物等的传质过程[1～3]。已往资料揭示,土壤中黏土矿物是DOM的重要吸附质;但迄今,有关DOM在不同类型黏土矿物表面吸附的差异及机制尚很不清楚。另外,不同DOM组分在土壤矿物上的吸附各异,土壤矿物对DOM不同成分的吸附具有选择性;因此分离DOM不同组分,分别研究其在土壤矿物上的吸附有助于揭示DOM与土壤矿物的结合机理,但该研究尚待深化。此外,目前研究中DOM多以土壤中提取的为主[4],对于因污泥农用等农业管理措施而从外部引入土壤的DOM的研究还较     

土壤矿物对有机质的吸附与固定机制研究进展

鉴于土壤有机质在生态系统及碳储存方面的重要性,关于土壤矿物对土壤有机质的吸附与固定机理方面的研究越来越受到了学术界的广泛关注。本文综述了近年来报道较多的土壤矿物对土壤有机质的吸附机制,以及主要影响因素。在众多矿物类型中,水合铁、铝氧化物及黏土矿物对有机质的吸附性较强,配体交换、络合、氢键、阳离子桥接、缩合及范德华力作用是土壤矿物与有机质之间的主要作用机制。土壤pH是影响矿物表面电荷及吸附位点的关键因素,进而影响矿物对有机质的吸附。土壤矿物表面的有机质含量对其继续吸附有机质具有一定的影响。吸附态有机质大多呈层状结构,越接近矿物表面的有机质与土壤矿物的结合越紧密。土壤有机质的稳定性受有机质与矿物间的作用力影响,一般而言,以化学键合吸附在矿物表面的有机质最稳定,其次为直接与矿物表面作用的电子"供体-受体"机制,范德华力和静电作用稳定性较差。近年来,随着分析设备和技术的进步,一些新的表征与探测方法(如热重分析、差示扫描量热法、傅里叶转换红外光谱、扫描电子显微镜、原子力显微镜、扫描透射X射线显微镜、中子散射技术等)被用于"矿物-有机质"结合机制的研究中,这些新手段毫无疑问会帮助更好地认识矿物与有机质间的作用机理。关于微生物在矿物吸附有机质、"矿物-有机质"复合体形成和演化过程中所起的作用,研究相对较少,但很明显这是至关重要的。     

铬在土壤中的吸附解吸研究进展

对铬在土壤中的吸附解吸研究进行了综述,土壤中铬的吸附解吸机理包括非专性吸附(离子交换吸附)、专性吸附以及物理表面吸附,分别对pH、氧化还原电位、土壤组分(土壤矿物和有机质)、竞争离子以及离子强度等因素对铬吸附解吸的影响作了论述。文章进一步描述了土壤中铬吸附解吸的数学模型Freundlich方程、Langmuir方程、一级动力学模型、金属-腐殖酸模型(one-sitemodel)和表面络合模型-扩散层模型(DLM)等的研究情况,并对今后的研究方向进行了探讨。     

磺胺嘧啶在土壤及土壤组分中的吸附/解吸动力学

抗生素在土壤中的吸附/解吸及迁移过程受其理化性质的强烈影响,其中土壤中的矿物成分,如高岭石、蒙脱石及腐殖酸等是重要控制因素。本文主要研究了磺胺嘧啶在土壤、高岭石、蒙脱石和腐殖酸中的吸附/解吸动力学过程,并对反应前后的高岭石、蒙脱石和腐殖酸进行傅里叶红外光谱(Fourier transform infrared, FTIR)表征,探讨其可能的吸附机理。结果表明:磺胺嘧啶的吸附(解吸)动力学过程,可以分为快速吸附(解吸)、吸附解吸动态平衡和吸附(解吸)平衡3个阶段;磺胺嘧啶在土壤及其3种组分中的吸附(解吸)均可在24 h内达到平衡,其浓度高低会导致土壤及其组分的吸附差异,不同土壤组分中的官能团含量、带电性质及氢键是造成吸附差异的主要原因;分别用伪一级动力学模型、伪二级动力学模型和Elovich模型对其吸附过程进行拟合,其动力学吸附过程更符合伪二级动力学模型,R20.99,主要受控于物理化学吸附;FTIR图谱表明磺胺嘧啶与高岭石以物理吸附为主,并有少量氢键作用,与蒙脱石之间主要以氢键作用完成吸附,而在腐殖酸中存在表面络合和π–π共轭作用。     

铁铝氧化物–层状硅酸盐矿物互作对Cr (Ⅵ)和As (Ⅴ)吸附的影响

以高岭石、蒙脱土、针铁矿和三水铝石四种单一典型土壤矿物以及针铁矿-蒙脱石和三水铝石-蒙脱石（质量比为1:1）两种代表性土壤矿物复合体为吸附材料，采用吸附平衡实验、能谱分析（(EDS）、红外光谱、扫描电镜、酸碱滴定和zeta电位测定等方法，研究了铁铝氧化物与层状硅酸盐矿物之间的相互作用对Cr(Ⅵ)和As(Ⅴ)吸附的影响及其机制。吸附平衡实验和EDS实验结果表明，两种复合体对Cr(Ⅵ)和As(Ⅴ)的吸附容量均小于其两种组成矿物单一体系吸附量的平均值，即铁铝氧化物与蒙脱石的互作降低了这些氧化物对Cr(Ⅵ)和As(Ⅴ)的吸附能力。表面性质表征结果表明，与蒙脱石复合后，针铁矿与三水铝石表面的正电荷均被完全中和，电荷符号发生反转。与理论值相比，三水铝石-蒙脱石复合体的表面位点总浓度无明显变化，比表面积减小。针铁矿-蒙脱石复合体的比表面积与理论值无明显差异，但矿物表面位点浓度减小，表面羟基红外吸收峰强度减弱。氧化物与层状硅酸盐矿物互作改变了矿物表面性质，这可能是导致氧化物对Cr(Ⅵ)和As(Ⅴ)的吸附能力降低的主要原因。当评估污染元素在土壤中有效性时应当考虑土壤固相组分间的互作对离子吸附的影响。     

镉污染水稻秸秆生物炭对土壤中镉稳定性的影响

中国农田土壤镉等重金属污染问题突出,对其生产过程中产生的镉污染水稻秸秆进行无害化和资源化利用研究具有重要意义。该研究通过连续提取试验、风险评价指数法、吸附动力学/热力学、土柱试验,以及X射线衍射分析、傅里叶变换红外光谱分析等手段,探究了不同热解温度下制备的镉污染水稻秸秆生物炭对土壤中Cd的稳定特性。研究结果表明,镉污染水稻秸秆热解制备的生物炭可有效吸附土壤镉。热解温度显著影响生物炭对Cd的吸附能力（P<0.05）,高温生物炭对Cd吸附容量大,700 ℃下制备的生物炭对Cd的吸附容量可达72.57 mg/g。生物炭对Cd的吸附主要通过含氧官能团表面络合和碳酸盐共沉淀吸附,其吸附过程符合Langmuir方程和准二级动力学模型,吸附过程受化学速率控制。土柱试验表明,镉污染水稻秸秆生物炭能有效降低土壤Cd的下渗迁移能力,其作用机制主要是将土壤Cd从酸可提取态转化为残渣态,施入高温生物炭的土壤中Cd的残渣态比例最高。上述结果表明,热解可有效处理镉污染水稻秸秆,制备的生物炭可用于Cd等重金属污染土壤的稳定修复,有效解决镉污染水稻秸秆的潜在二次污染问题并实现其安全利用。     

土壤镉吸附的研究进展

综述了土壤镉吸附的机理和土壤pH、有机质含量、粘粒矿物类型及含量、土壤溶液中竞争性阳离子、共存阴离子、土壤温度等土壤性质对土壤镉吸附的影响；总结了土壤镉的吸附量随土壤pH增加、温度升高及有机质、铁锰氧化物和粘土矿物含量增加而增加的机理；竞争性阳离子的存在抑制镉的吸附，土壤溶液中共存阴离子对镉吸附的影响取决于阴离子种类和土壤类型。     

蒙脱石-氧化铁二元复合胶体吸附钨的研究

本研究选取代表性层状硅酸盐蒙脱石，两种代表性氧化铁(水铁矿、针铁矿)，合成蒙脱石-水铁矿、蒙脱石-针铁矿二元复合体，通过宏观吸附以及光谱学技术探究钨(WO₄^2-)在蒙脱石-氧化铁复合体上的吸附行为和潜在机制。结果表明：氧化铁紧密覆盖在蒙脱石表面，使表面颗粒更加细小；钨的吸附量随pH升高而降低，3种吸附剂对钨吸附量大小顺序为：蒙脱石-水铁矿>蒙脱石-针铁矿>蒙脱石；原位红外光谱实验表明，钨在蒙脱石表面主要以外圈络合物形式存在，而在蒙脱石-氧化铁复合体上形成内圈络合物(Fe-O-W)，且在低pH时，形成聚合态钨；X-射线光电子能谱进一步表明，针铁矿和水铁矿表面铁羟基参与了钨的络合反应。本研究证实，氧化铁覆盖不仅增大蒙脱石对钨的吸附量，而且使钨由外圈络合物形态转变为内圈络合态，进一步生成聚合态钨。研究结果对预测钨在土壤中的迁移转化、生物有效性和归宿有重要指导意义。     

天津半干旱地区不同种植年限菜田土壤微生物变化特征的研究

对天津周边半干旱地区不同种植年限的菜田土壤微生物状况调查研究表明 ,该地区土壤微生物以细菌为主 ,夏季微生物总量大大高于冬季 ;随着种菜年限的增加 ,耕层和亚耕层微生物总量都有增加趋势 ,其中细菌和放线菌增加明显 ,真菌有下降趋势 ;真菌类群分析表明 ,少数纤维素分解菌 ,如青霉 (Penicillium)、木霉 (Trichoderma)等为优势菌 ,而糖和木质素分解菌仅占少数。用尖孢镰刀霉 (Fusariumuoxysporum)、大肠杆菌 (Escherichia coli)接种不同种菜年限土壤 ,检测土壤拮抗菌状况发现 ,拮抗菌仅在种植年限长的老菜田的放线菌中发现。表明北方半干旱地区菜田土壤细菌为优势菌 ,主要存在于土壤微孔隙中 ;而适于生活在土壤疏松大孔隙中的真菌数量极少。应注意土壤结构的改良 ,为丰富土壤微生物提供良好的生态环境     

天津半干旱地区不同种植年限菜田土壤微生物变化特征的研究

对天津周边半干旱地区不同种植年限的菜田土壤微生物状况调查研究表明 ,该地区土壤微生物以细菌为主 ,夏季微生物总量大大高于冬季 ;随着种菜年限的增加 ,耕层和亚耕层微生物总量都有增加趋势 ,其中细菌和放线菌增加明显 ,真菌有下降趋势 ;真菌类群分析表明 ,少数纤维素分解菌 ,如青霉 (Penicillium)、木霉 (Trichoderma)等为优势菌 ,而糖和木质素分解菌仅占少数。用尖孢镰刀霉 (Fusariumuoxysporum)、大肠杆菌 (Escherichia coli)接种不同种菜年限土壤 ,检测土壤拮抗菌状况发现 ,拮抗菌仅在种植年限长的老菜田的放线菌中发现。表明北方半干旱地区菜田土壤细菌为优势菌 ,主要存在于土壤微孔隙中 ;而适于生活在土壤疏松大孔隙中的真菌数量极少。应注意土壤结构的改良 ,为丰富土壤微生物提供良好的生态环境     

沈阳市城市表土中微生物区系变化的初步研究

在沈阳市远郊-近郊-市区等不同城市化水平区内选取林地、草地和路边土几种不同利用方式下的表层土壤,对土壤中的微生物状况进行了初步分析。结果表明,随着城市化水平的提高,土壤中微生物的数量表现为明显的减少趋势。其中变化较大的是细菌,而真菌和放线菌的变化不明显。     

Sediment denitrification in waterways in a rice-paddy-dominated watershed in eastern China

Purpose

Rice-paddy-dominated watersheds in eastern China are intensively cultivated, and lands with two crops receive as much as 550–600 kg?ha^–1?year^–1 of nitrogen (N), mainly through the addition of N-based fertilizers. However, stream N concentrations have been found to be relatively low. Waterways in the watersheds are assumed to be effective “sinks” for N, minimizing its downstream movement. We directly measured net sediment denitrification rates in three types of waterways (ponds, streams/rivers, and a reservoir) and determined the key factors that control net sediment denitrification. Such information is essential for evaluating the impact of the agricultural N cycle on the quality of surface water.

Materials and methods

The pond–stream–reservoir continuum was sampled every 2 months at nine sites in an agricultural watershed between November 2010 and December 2011. Net sediment N₂ fluxes/net sediment denitrification rates were determined by membrane inlet mass spectrometry and the N₂/Ar technique. A suite of parameters known to influence denitrification were also measured.

Results and discussion

Net denitrification rates ranged between 28.2?±?18.2 and 674.3?±?314.5 μmol N₂–N?m^–2?h^–1 for the streams, 23.7?±?23.9 and 121.2?±?38.7 μmol N₂–N?m^–2?h^–1 for the ponds, and 41.8?±?17.7 and 239.3?±?49.8 μmol N₂–N?m^–2?h^–1 for the reservoir. The mean net denitrification rate of the stream sites (173.2?±?248.4 μmol N₂–N?m^–2?h^–1) was significantly higher (p?<?0.001) than that of the pond sites (48.3?±?44.5 μmol N₂–N?m^–2?h^–1), and the three types of waterways all had significantly higher (p?<?0.01) mean net denitrification rates in summer than in other seasons. Linear regression and linear mixed effect model analysis showed that nitrate (NO₃ ^?–N) concentration in surface water was the primary controlling factor for net sediment denitrification, followed by water temperature. Using monitoring data on NO₃ ^?–N concentrations and temperature of the surface water of waterways and an established linear mixed effect model, total N removed through net sediment denitrification in the pond–stream–reservoir continuum was estimated at 46.8?±?24.0 t?year^–1 from July 2007 to June 2009, which was comparable with earlier estimates based on the mass balance method (34.3?±?12.7 t?year^–1), and accounted for 83.4 % of the total aquatic N. However, the total aquatic N was only 4.4 % of the total N input to the watershed, and thus most of the surplus N in the watershed was likely to be either denitrified or stored in soil.

Conclusions

High doses of N in a rice-paddy-dominated watershed did not lead to high stream N concentrations due to limited input of N into waterways and the high efficiency of waterways in removing N through denitrification.     

Trends in soil science in Switzerland

Phytoremediation is an emerging technology based on the use of green plants to remove, contain, inactivate or destroy harmful environmental pollutants. Recent developments in Europe and the USA show that the approach is somewhat different on both sides of the Atlantic. In Europe, phytoremediation has more basically been research driven and, based on the outcomes, applications have been envisaged. By contrast, the approach in the USA is more application and experience driven. In spite of a growing track record of commercial success, more demonstration projects are needed to prove that phytoremediation is effective in order to rigorously measure its underlying economics, and to expand its applications. More fundamental research is also required to better understand the complex interactions between pollutants, soil, plant roots and micro-organisms at the rhizosphere level, to increase the bioavailability of pollutants, to fully exploit the metabolic diversity of plants and, thus, to successfully implement this new green technology.     

Trace metals in precipitation in Sweden

Trace metals (Cd, Cu, Fe, Mn, Pb, and Zn) concentrations in atmospheric precipitation have been routinely monitored in Sweden since the autumn of 1983. Concentrations are highest in southern Sweden and decrease northward. It is postulated that the long range transport of anthropogenic pollutants from the rest of Europe is the major source of Cd, Pb, and Zn in precipitation. Evidence for this hypothesis is that enrichment factors indicate anthropogenic origin, and Swedish atmospheric emissions of Zn and Cd are 2 to 3 times smaller than deposition fluxes. Also, Cd, Pb, and Zn concentrations are correlated in both space and time and are also well correlated with exSO₄ ⁺, a substance known to be of anthropogenic origin transported long distances.     

Patterns in trace elements in lichens

Water, Air, & Soil Pollution - Epiphytic lichens were sampled in a Dutch national monitoring survey, which was carried out twice within 5 yr. The samples were analyzed by neutron activation...     

中国华北地区近40年物候春季变化

根据华北地区7个观测站物候资料,分析了华北地区1963-1996年及北京1963-2005年物候春季的变化特征及其与气温的关系。结果表明:华北地区的物候春季有明显提早来临的趋势,而造成这一变化的主要因素是本地区近40 a来冬春季气温的明显上升。其中1963-1996年间华北地区1-3月及4月的平均气温分别上升了2.3℃与1.7℃,物候春季起止日期分别提前了9d和4d,因而使得春季长度也延长了5d;北京1963-2003年间1-3月及4月的平均气温分别上升了3.5℃与2.6℃,物候春季的起止日期分别提前了11d和10d,但春季长度没有明显变化。     

Longitudinal changes in dietary intake in Scottish women around the menopause: changes in dietary pattern result in minor changes in nutrient intake

Objective: To examine dietary change that has occurred over 5 to 6 years.Subjects: A cohort of Scottish women (n=898) with a mean age of 47.5 years (range 45-54 years) at baseline.Design: Dietary intake was assessed by validated food-frequency questionnaire (FFQ) and analysed using the UK Composition of Foods database.Results: Since the first dietary assessment, mean daily energy intake had decreased from 8.2+/-2.3 to 7.9+/-2.2 MJ. The degree of low energy reporting (defined as ratio of energy intake to basal metabolic rate <1.1) had increased from 18.7% at baseline to 25.6% at follow-up. Low energy reporters were significantly heavier than 'normal' energy reporters (mean weight at follow-up, 68.9+/-12.6 vs. 66.8+/-11.3 kg) and could be deliberately restricting intake rather than underreporting. Overall there were decreases in intakes of red meat, processed meat and cheese, but increases in poultry and non-oily fish consumption. Consumption of bread, biscuits and cakes had gone down and there was an increase in cereal and rice/pasta consumption. Intake of potatoes had decreased whereas fruit intake had increased. There were small but statistically significant differences in intakes for most nutrients (<8% change). Nutrient intakes at both visits were similar across menopausal status and usage groups of hormone replacement therapy. Modifications to the computer version of the McCance and Widdowson nutrient database, which differed from the published version, were noted. These changes altered the original baseline values for our study.Conclusions: The menopause per se is not a period of marked change in nutrient intake. Caution is advised when using computer databases of food compositions for longitudinal studies.     

闽北不同土地利用方式径流量动态变化特征

采用定位研究方法和小集水区试验技术方法,通过两年的降雨量数据观测,对闽北地区木荷林地、杉木林地、封山育林地和对照等不同土地利用方式的小集水区进行坡面径流动态规律研究。研究结果表明:试验小区地表径流的产生主要是受降雨量的影响,而与降雨强度的关系不大,地表径流量与降雨量之间呈现出极显著的非线性二次抛物线关系(P<0.01)。4种不同土地利用方式的月平均径流量一般随月降雨量的增大而增大,并且在同1月份间其平均地表径流量的大小趋势为:对照>封山育林>杉木>木荷,均是在6月份达到最大值,9月份出现最小值。对照比木荷林地、杉木林地、封山育林地更容易产生地表径流,林地具有较好的涵养水源和保持水土作用。