澳门城市垃圾焚烧底灰的重金属淋溶及其遗传毒性评价

应用美国国家环境保护局推荐的毒性特性溶出程序(toxicitycharacteristicleachingprocedure,TCLP),以及ICP-MS和ICP-AES技术研究了澳门城市垃圾焚烧底灰中重金属的淋溶,并结合蚕豆根尖微核试验评价了其潜在的生态与健康风险.结果显示,该底灰淋溶出来的重金属元素:铝(Al)、锰(Mn)、钴(Co)和汞(Hg)的浓度低于0.01mg·L-1,铁(Fe)、铜(Cu)和钼(Mo)的浓度低于0.1mg·L-1,而铬(Cr)、锌(Zn)、硒(Se)、锶(Sr)、钡(Ba)和铯(Cs)的浓度在0.11mg·L-1￣2.19mg·L-1之间.需要注意的是淋溶液中铅(Pb)的浓度异常高,最高可达19.06mg·L-1,超过了美国相关标准的上限(5mg·L-1);对比不同条件下底灰中重金属的淋溶情况,表明溶解作用和淋溶液的pH值是影响其淋溶的2个重要因素.蚕豆根尖微核试验显示各淋溶液处理组根尖细胞微核率明显升高,与阴性对照组相比具有显著性差异(p<0.05),表明各淋溶液具有遗传毒性;随着淋溶液中重金属浓度的增加,蚕豆根尖细胞所表现出来的毒性效应增强,表明重金属是淋溶液具有遗传毒性的重要原因.     

The ecology of energy and nutrient fluxes in hemlock forests invaded by hemlock woolly adelgid

The hemlock woolly adelgid (HWA, Adelges tsugae Annand) is currently causing a severe decline in vitality and survival of eastern hemlock in North American forests. We analyzed the effects of light HWA infestation on vertical energy and nutrient fluxes from the canopy to the forest floor. Canopy throughfall, litter lysimeters, and laboratory litter microcosms were used to examine the effects of HWA-affected and unaffected throughfall on litter type, leachate, and litter chemistry. Early in the season adelgid infestation caused higher dissolved organic carbon (DOC; +24.6%), dissolved organic nitrogen (DON; +28.5%), and K (+39.3%) fluxes and lower inorganic nitrogen fluxes (-39.8%) in throughfall and in adjacent litter solutions collected beneath infested compared to uninfested trees. Needle litter collected beneath uninfested hemlock had significantly lower N concentrations compared to needles collected beneath infested trees, while no difference in N concentrations was found in birch litter. Bacteria were significantly more abundant on hemlock and birch litter beneath infested trees, while yeasts and filamentous fungi showed no consistent response to HWA throughfall. Litter microcosms showed that less DOC was leaching from birch than from hemlock needles when exposed to HWA throughfall. Overall, NH4-N and DON leachate concentrations were higher from birch than from hemlock litter. Thus, HWA-affected throughfall leads to qualitative and quantitative differences in nitrogen export from the litter layer. The N concentration of hemlock litter did not change with time, but the N concentration in birch litter increased significantly during the course of the experiment, especially when HWA-affected throughfall was applied. We suggest a nonlinear conceptual model for the temporal and vertical transition of energy and nutrient fluxes relative to progressing HWA infestation from a pure hemlock to a birch/maple-dominated forest. Progressive needle loss and changes in needle chemistry are likely to produce a humped-shaped DOC curve, while N fluxes initially decrease as infestation continues but rise eventually with hemlock decline and immigration of hardwood species. These findings suggest that it is necessary to understand the biology and specific physiological/trophic effects of exotic pests on their hosts and associated ecosystem processes in order to decipher the temporal dynamics, direction of change, and functional consequences.     

模拟降水对碱性盐化土壤中镉的淋滤及形态变化的影响

采用人工模拟方式,试验研究了不同pH值的降水对碱性盐化土壤中镉的连续淋滤效果,分析了淋洗后土壤中镉的形态变化特征。结果表明,在不同pH值降水对土壤中镉的淋滤过程中,12h内基本上达到高峰,12h后镉的淋滤量较低,随着时间的延续镉的淋洗量基本保持不变;降水有利于土壤中的镉释放,且pH值越低,镉的释放量越高。土壤盐化对降水淋洗镉的效果有一定影响,氯化物的存在,有利于镉的淋滤,淋滤量增加值在18%～94%之间,随着淋洗液pH值的增加,镉的淋滤量增加幅度减少;与对照组土壤样品相比,淋洗液pH降低利于增大硫酸盐型盐化土壤中镉的淋滤量,当pH值为中性时,镉的淋滤量减少;苏打型盐化土壤镉的淋洗效果与硫酸盐型土壤相似。模拟降水淋洗后,土壤中镉的形态发生明显变化,与淋洗前相比,土壤中镉的可交换态、碳酸盐结合态、有机结合态的质量分数降低,随着淋洗液酸性的增加,降低幅度增大;镉的铁锰氧化态相对质量分数在淋洗后有所增加。     

鼎湖山针阔叶混交林土壤酸度与土壤养分的季节动态

研究了鼎湖山南亚热带森林演替系列中处于中间阶段的针阔叶混交林土壤的pH值、水解氮、速效磷、钾、交换性钙、镁等几种营养元素的含量现状及季节动态。结果表明：混交林土壤为强酸性土壤，表层(0--20cm)土壤酸度高于中(20--40cm)、下(40-60cm)层土壤，0～40cm土壤pH值具有明显的季节波动性。降雨、温度、凋落物、植物根系以及微生物的活动等因素可能是鼎湖山混交林土壤pH值季节动态变化的主要因素。除Ca外，在同一剖面内，表层土壤养分的含量明显高于中下层，而中下层之间相差不大，养分大多在冬季较高，随着季节变动(1，4，7，10月)呈下降趋势。     

色谱自动进样瓶可溶出砷对样品砷形态测定的影响

选用几种常用玻璃色谱自动进样瓶(简称色谱瓶),包括硼硅玻璃、一级水解级玻璃和高白料玻璃色谱瓶,以及聚丙烯材质的色谱瓶,1%HNO3对色谱瓶浸提后用ICP-MS和HPLC-ICP-MS测定浸提液中砷的总量和形态,并研究了10%HNO3对色谱瓶的清洗效果;此外还探讨了温度及时间对玻璃色谱瓶中砷释放的影响.结果表明,玻璃色谱瓶中砷普遍存在,其中硼硅玻璃色谱瓶浸提液中砷浓度低于1μg·L-1,用10%HNO3酸泡24 h能够全部清除;而一级水解级玻璃和高白料玻璃色谱瓶浸提液中砷的浓度则高达45.67μg·L-1和70.25μg·L-1,酸泡24 h后也有较高的残留量,浓度分别为1.63μg·L-1和0.94μg·L-1.高温能促进玻璃色谱瓶中砷的释放;玻璃色谱瓶中砷的释放量随时间的延长而增加,但短时间内即达到平衡.形态分析结果表明,玻璃色谱瓶浸提液中砷形态为As(Ⅴ),没有检测到As(Ⅲ)、二甲基砷酸(DMA)和甲基砷酸(MMA).同时,聚丙烯色谱瓶浸提液中砷总量低于检测限,因而在进行砷形态测定时,建议使用聚丙烯色谱瓶或者经10%HNO3清洗后的硼硅玻璃色谱瓶,以避免玻璃色谱瓶中As(Ⅴ)的污染.     

Regression equations for estimating throughfall nutrient fluxes using wet deposition data and their applicability for simulating the soil acid–base status using the dynamic forest soil–atmosphere model SAFE

Throughfall may contribute large amounts of nutrients to forest soils via the leaching of accumulated dry particulates on the canopy, and by altering incoming precipitation, it may have some control on the acid–base status of the soil. Unfortunately, information about throughfall in forests is sparse and thus, scientists must deal with this gap in knowledge before conducting regional applications of dynamic soil acidification models. The first objective of this paper was to test the possibility of developing regression equations that could allow modellers to estimate throughfall nutrient fluxes using wet deposition nutrient fluxes as input data. The second objective was to test the relative importance of this simplification on regional applications of the dynamic soil–atmosphere model Soil Acidification in Forested Ecosystems (SAFE) using one published application of this model as the base case. Annual throughfall nutrient fluxes were estimated successfully from annual wet deposition fluxes for individual ions. The success of these relationships were however inversely proportional to the intensity at which an ion was involved in exchange reactions: models generally performed better with more conservative ions. The simulation of the soil acid–base status with SAFE suggested that it was appropriate to use the throughfall estimates yielded using the regression equations. Also, testing of the SAFE output using different regression equations in throughfall showed that, in the case of base cations, the key for modelling the soil acid–base status was to produce accurate throughfall estimates of Ca and Mg, and that K had marginal effects. However, a small bias in solution pH was introduced as the balance between alkalinity and acidity in the different categories of deposition appeared to be diverging from the base case (measured) values. The use of our approach at other sites may indicate if there is a systematic bias or not in the regressions. Yet, results suggest that the regression equations are appropriate for the purpose of modelling the soil acid–base status at the scale of the landscape because it assures that the same set of assumptions in throughfall are used for each application.     

生物质气化发电厂灰渣中微量元素的赋存形态及其析出

分别用Tessier逐级提取形态分离法和模拟酸雨浸提实验,研究了生物质气化发电厂的气化器、淋洗器和旋风分离器底灰中微量元素的赋存形态及其析出规律,探讨了微量元素析出浓度和影响其析出的因素．结果表明,微量元素大部分存在于残渣态,其有机态、Fe-Mn氧化态和碳酸盐结合态的浓度依次减少,可交换态的赋存量极低;元素的析出受浸提液pH值、浸提温度和浸提时间的影响,元素在灰渣颗粒物中的赋存形态及含量的高低也影响元素的释放和析出程度．     

模拟酸雨对红壤铝形态的影响

用动态淋洗试验，研究了不同pH的模拟酸雨对红壤中铝形态和性质的影响．结果表明，酸雨淋洗引起红壤中盐基离子的淋失和土壤铝的溶出．随着酸雨溶液pH的降低，盐基淋矢量和铝溶出量增加．酸雨淋洗影响土壤铝形态的转化，使红壤中交换态铝上升，吸附态羟基铝有所下降．这说明在酸雨长期作用下，羟基铝溶解，并转化为交换态铝和引起铝的溶出，使铝进入环境，危害生态系统．     

模拟酸雨对石灰岩的破坏和表面腐蚀

硫酸是酸雨中腐蚀石灰岩的最主要成分,以不同pH值(4.0,5.6)的稀硫酸溶液模拟酸雨对石灰岩进行淋溶处理,研究不同酸度酸雨对石灰岩腐蚀的影响,包括溶液中pH值变化,Ca2+离子浓度变化、石灰岩表面粗糙度变化、重量损失和表面结构变化.结果表明,不同酸度酸雨淋溶后石灰岩都受到一定程度的影响,随着模拟酸雨酸度的增大,Ca2+的释放量呈上升趋势;Ca2+溶出速率,与H+的消耗速率不呈现明显的相关关系;经过120 h酸雨淋溶后,石灰岩重量损失率在0.083%～0.25%.酸雨淋溶后石灰岩表面结构产生了腐蚀,表面粗糙度增加,孔隙变深变宽,并在一定程度上缓解了酸雨的进一步腐蚀.表明高酸度雨水对南京六朝石刻等石灰岩建筑有影响.     

A Critical Appraisal of Field Evidence From A Regional Survey for Acid Deposition Effects On Scottish Moorland Podzols

Samples have been collected from major horizons of 34 podzol profiles distributed throughout Scotland, all developed from granite or granitic tills and under Calluna moorland. the pH in water and calcium chloride pastes, exchangeable cations and cation exchange capacity, and extractable aluminium of the soils collected have been measured, and the results studied in relation to reported atmospheric deposition of H⁺, non-marine sulphur and nitrate. for all horizons, significant positive correlations were found between soil pH and rainfall mean pH, as might be expected when the critical load of H⁺ deposition is exceeded. Acidifying pollutant deposition also apparently increased soil extractable aluminium concentrations in the B and C horizons. However, exchangeable base cation concentrations tended to increase, rather than decrease, with increasing precipitation acidity. This effect was attributed to increases in biogeochemical cycling of base cations, increases in leaching inputs of base cations from overlying A/E horizon soils, and increases in the inputs of base cations leached from upslope. the results suggest that the simple steady state mass approach to the quantification of critical loads, as often applied, may be an oversimplification.     

A Critical Appraisal of Field Evidence From A Regional Survey for Acid Deposition Effects On Scottish Moorland Podzols

Samples have been collected from major horizons of 34 podzol profiles distributed throughout Scotland, all developed from granite or granitic tills and under Calluna moorland. the pH in water and calcium chloride pastes, exchangeable cations and cation exchange capacity, and extractable aluminium of the soils collected have been measured, and the results studied in relation to reported atmospheric deposition of H⁺, non-marine sulphur and nitrate. for all horizons, significant positive correlations were found between soil pH and rainfall mean pH, as might be expected when the critical load of H⁺ deposition is exceeded. Acidifying pollutant deposition also apparently increased soil extractable aluminium concentrations in the B and C horizons. However, exchangeable base cation concentrations tended to increase, rather than decrease, with increasing precipitation acidity. This effect was attributed to increases in biogeochemical cycling of base cations, increases in leaching inputs of base cations from overlying A/E horizon soils, and increases in the inputs of base cations leached from upslope. the results suggest that the simple steady state mass approach to the quantification of critical loads, as often applied, may be an oversimplification.     

模拟氮沉降对森林土壤化学性质的影响

大气氮沉降的增加对森林土壤的影响是近来生态学研究的重要课题。以鼎湖山季风常绿阔叶林（以下简称为“阔叶林”）、马尾松（Pinus massoniana）林、针阔叶混交林（以下简称为“混交林”）和增城木荷（Schima superba）人工幼林等4种林型土壤为研究对象,采用野外原位模拟大气氮沉降的方法,设置3种模拟氮沉降量,即N0（对照,N：0 g·m-2·a-1）、N5（N：5 g·m-2·a-1）、N10（N：10 g·m-2·a-1）,在模拟氮沉降时间分别为42个月（阔叶林）、31个月（马尾松林）、50个月（混交林）、20个月（人工幼林）后,采集0~20 cm土层的林地土壤,分析土壤的化学性质,探讨不同氮沉降量对不同林型土壤化学性质的影响。结果表明,（1）模拟氮沉降对鼎湖山阔叶林、马尾松林、混交林土壤pH值的影响基本一致,均使pH值下降。其中,当氮沉降量达到N10时,阔叶林土壤pH值降为3.97,与对照相比下降了0.11 pH单位,差异达显著性水平（p〈0.05）。而人工幼林土壤pH值未随着氮沉降量的不同而有明显的变化。（2）模拟氮沉降在近2年至4年的时间内,对阔叶林、混交林、人工幼林的土壤有机质、全氮、全磷、全钾、水解性氮、速效磷、速效钾含量的影响均不明显,马尾松林土壤有机质、全氮、全磷、速效磷、速效钾含量也没有明显变化,但模拟氮沉降导致了马尾松林土壤水解性氮含量明显下降,从95.12 mg·kg-1降至84.39 mg·kg-1,差异达显著性水平（p〈0.05）。（3）模拟氮沉降对鼎湖山阔叶林、马尾松林、混交林等3种林型土壤盐基饱和度、盐基离子Ca2＋、Mg2＋、K＋含量的影响未达显著水平,而对这3种林型土壤交换性Na＋含量的影响则较明显且影响趋势基本一致,即氮沉降的增加导致了土壤交换性Na＋含量明显下降。在N10处理下,与对照相比,这3种林型的土壤交换性Na＋含量分别下降了40.0%、68.4%、50.0%,差异达显著性水平（p〈0.05）。氮沉降对人工幼林土壤盐基离子含量无明显的影响。由此可得出结论：在近2年至4年的时间内,氮沉降的增加能引起鼎湖山3种林型土壤尤其是阔叶林土壤加速酸化,引起交换性Na＋明显淋失,以及马尾松林土壤水解性氮含量明显下降;但氮沉降的增加对木荷人工幼林土壤化学性质暂无明显的影响。后者可能与该林型模拟氮沉降时间较短、林龄较轻而处于快速生长期等因素有关。     

改性污泥对矿区铜、镉污染土壤的修复

城市污泥的重金属含量超标是限制其资源化利用的主要瓶颈,论文采用石灰＋硫粉＋生物淋滤的方法去除重金属,制备改性污泥,探讨其对矿区Cu、Cd污染农田土壤的修复效果,以期实现以废治污的目标。供试水稻土采自江西某矿区附近农田,土壤Cu和Cd的TCLP（Toxicity characteristic leaching procedure）浸出量分别为40.34 mg·kg-1和660.1μg·kg-1,其中Cu的质量分数超过国际标准值15 mg·kg-1。通过室内土培的方法,将改性污泥分别按土重的0%、1%、3%、5%和10%施入供试土壤培养30 d后,分析土壤Cu和Cd的活性、形态变化以及土壤蛋白酶和脲酶活性等指标评价改性污泥对污染土壤的修复效果及作用机理。结果表明,改性污泥对土壤Cu产生显著的钝化作用,且各施用量对Cu的有效态含量表现出显著差异。当改性污泥的用量为土重的5%时,Cu的有效态含量降至12.03 mg·kg-1,低于国际标准。改性污泥对土壤Cd的钝化效果相对较弱。当改性污泥的用量为1%时,土壤Cd的活性反而有所增加。当改性污泥的用量为5%时,Cd的活性显著降低,土壤Cd的浸出量降至539.6μg·kg-1。土壤重金属形态分析的结果表明,土壤Cu主要以碳酸盐结合态、有机结合态和残渣态存在。改性污泥用量增加,可交换态Cu含量下降,当改良剂用量为土重的5%时,可交换态Cu由8.10%降至4.10%。相反,有机结合态Cu含量由26.45%增加至32.34%。土壤的可交换态Cd含量由36.80%降至30.69%。说明施用改性污泥,土壤可交换态Cu、Cd向有机结合态发生转化。土壤蛋白酶和脲酶的活性变化能较好地指示修复效果,且土壤脲酶的指示效果优于蛋白酶。     

模拟酸雨对酸性土壤铝溶出及其形态转化的影响

研究了我国南方酸沉降区主要土壤类型在模拟酸雨影响下，土壤中铝离子释放及铝形态转化的特点。结果表明，酸雨淋洗造成土壤中铝离子释放，酸雨pH值越低，铝离子释放量越大；酸雨淋洗还造成土壤中铝形态发生变化，酸雨pH越低，土壤中羟基态铝和腐殖质铝含量愈低，交换态铝含量越高，土壤中铝对植物和生态系统的危害性也越大。     

五指山不同海拔高度的土壤化学性质特征

根据海南省五指山2003年土壤样品的分析结果,对不同海拔高度下五指山土壤的化学性质特征进行了分析。结果表明,在不同海拔高度下水提pH和盐提pH随采样深度的增加基本呈明显的增大趋势,交换性H 、CEC、全N和有机质随采样深度的增加基本呈明显的下降趋势;而交换性Al3 和交换性酸除在720m、894m处剖面外,其它海拔高度下也基本随采样深度的增加而明显降低。从化学过程较为活跃的表层土壤来看,水提pH、盐提pH、交换性H、交换性Al3 和交换性酸随海拔高度的增加并没有明显的同时增大或减小的分布规律,而CEC、全N和有机质有明显的增加趋势。     

Heavy metals availability (Fe, Mn, Zn, Cu and Cr) in Aden Gulf sediments under aerobic and anaerobic conditions

The present study aims to analyse the chemical speciation of heavy metals in relation to aerobic and anaerobic conditions. Two sediment samples (from the Gulf of Aden, Yemen) were incubated under flooded conditions. In particular, the chemical forms of Fe, Mn, Zn, Cu and Cr under the experimental conditions were studied using a sequential chemical extraction method. The pH and Eh of the suspension were measured as critical parameters controlling the fate of the metals in the environment. The results showed that the metals concentration in the different forms varied with time incubation and affected by the variation of redox potential and pH value. Also, the changes in both redox potential (Eh) and pH values had evident effects on heavy metals transformation. It is obvious that the highest redox potential affected the amount of iron and manganese in the oxides form. When the redox potential decreased to-133 and-170 mV, it caused a significant transformation of the Fe-Mn oxide form to the water-soluble and exchangeable fractions. Under anaerobic conditions, the relative percentage of all five metals including the summation of four fractions (the water-soluble and exchangeable, carbonate, oxides and organic fractions) constituted 45-60% of the total amount of iron, 33-50% for manganese, 33-63% for Zn, 63-74% for Cu and 19-43% for Cr. Both zinc and copper among water-soluble and exchangeable fraction were high at the end of incubation period, this accompanied by a significant decrease in the content of the organically bound fraction. In general, the reducing conditions were more favorable for metal bound to water soluble and exchangeable fraction.     

模拟酸雨对森林红壤中铝的溶出及不同土层酸度变化的影响

为进一步探明酸沉降对森林红壤及生态环境的影响，模拟长沙地区降水酸度及离子组成，采用浸泡试验对两种森林红壤活性铝的释出及土壤理化性质的变化进行了研究。结果表明，模拟酸雨浸泡初期，土壤活性铝的释出量随浸泡次数的增加而增加，原始土壤pH值愈低，活性铝释出愈多；强酸度、高离子浓度（AR4）模拟酸雨对土壤中活性铝的溶出量远大于基础酸雨（AR3）及弱酸、低离子浓度酸雨（AR2）和对照酸雨（AR1）。模拟酸雨酸度愈大，对土壤pH值的影响愈明显，不同土层间，以A层土壤pH值下降最明显，B、C层土壤则下降较小。模拟酸雨模拟浸泡土壤25年后，土壤阳离子交换量均有不同程度下降，有机质含量高，原土壤阳离子交换量大的土壤下降幅度也大。     

Migration of manganese and iron during the adsorption-regeneration cycles for arsenic removal

Fe-Mn binary oxide incorporated into porous diatomite (FMBO-diatomite) was prepared in situ and regenerated in a fixed-bed column for arsenite [As(III)] and arsenate [As(V)] removal. Four consecutive adsorption cycles were operated under the following conditions: Initial arsenic concentration of 0.1 mg·L^-1, empty bed contact time of 5 min, and pH 7.0. About 3000, 3300, 3800, and 4500 bed volumes of eligible effluent (arsenic concentration≤0.01 mg·L^-1) were obtained in four As(III) adsorption cycles; while about 2000, 2300, 2500, and 3100 bed volumes of eligible effluent were obtained in four As(V) adsorption cycles. The dissection results of FMBO-diatomite fixed-bed exhibited that small amounts of manganese and iron were transferred from the top of the fixed-bed to the bottom of the fixed-bed during As(III) removal process. Compared to the extremely low concentration of iron (<0.01 mg·L^-1), the fluctuation concentration of Mn²⁺ in effluent of the As(III) removal column was in a range of 0.01–0.08 mg·L^-1. The release of manganese suggested that manganese oxides played an important role in As(III) oxidation. Determined with the US EPA toxicity characteristic leaching procedure (TCLP), the leaching risk of As(III) on exhausted FMBO-diatomite was lower than that of As(V).     

Untersuchung von Abfällen mit biologischen Testverfahren zur Bewertung der Wassergefährdung

Wastes from three different types of waste treatment facilities (slag from a municipal waste incineration plant, slag granules from a pilot plant combining carbonization and incineration, mechanical and biological treated wastes) were examined to determine their hazard potential to different waters sites. The process temperature is seen to be the main difference between the three treatment processes. The wastes were extracted with water according to the German standard DIN 38414 S 4 and additionally at a constant pH value of 4. The leachates were investigated in a battery of aquatic bioassays and characterised physically and chemically. Every leachate revealed in a toxic effect at least in one test. The toxicity of the leachates prepared at a pH of 4 was significantly higher than the toxicity of the leachates prepared by extraction with water without pH adjustment. The leachates of the slag granules showed the lowest toxicity. On the basis of these experimental results, a scheme to derive Water Hazard Classes of wastes, which is presented in part II of this publication, was developed.     

外加锌在土壤中形态的研究

本文采用化学逐级提取法对吸附锌后的土壤分别提取了交换态、CaCO_3结合态、氧化物结合态和有机质结合态的锌量,并讨论pH、温度和溶液中锌离子浓度对不同形态锌分布的影响。实验结果表明:外加锌被石灰性土壤吸附后,高pH值(7.5)时形态分布为:CaCO_3结合态≥交换态>氧化物结合态>有机质结合态;低pH值(5.5)时则为:交换态>CaCO_3结合态>氧化物结合态>有机质结合态。各形态锌的分配系数还受到吸附时的温度和溶液中锌离子浓度的影响。