几种重金属钝化剂及其不同添加比例对猪粪堆肥重金属(As,Cu,Zn)形态转化的影响

采用连续提取法研究了猪粪堆肥处理中重金属浓度和形态的变化以及不同添加比例的重金属钝化剂对其浓度和形态的影响.结果表明:经过堆肥处理后,重金属As,Cu和Zn的浓度普遍升高;堆肥处理能促进重金属As,Cu和Zn的形态向活性降低的方向转化,因此堆肥处理可以降低重金属的生物有效性.在3种重金属钝化剂及不同添加比例处理中,猪粪堆肥重金属As的最佳钝化剂及其添加比例为7.5%的粉煤灰,对可交换态As的钝化效果为51.4%;重金属Cu的最佳钝化剂及其添加比例为2.5%的粉煤灰,对可交换态Cu的钝化效果为29.7%;重金属Zn的最佳钝化剂及其添加比例为5.0%的钙镁磷肥,对可交换态Zn的钝化效果为50.0%.因此,堆肥处理中添加重金属钝化剂可以降低猪粪堆肥中重金属的有效性,有利于降低猪粪堆肥土地利用中重金属污染的风险.     

砂姜黑土中重金属Cu、Cd、Zn形态分布与土壤酶活性研究

采用小麦农田取样,对土壤中的重金属运用连续提取方法,研究了皖北砂姜黑土中Cu、Cd、Zn的化学形态特征及其与四种土壤酶(过氧化氢酶、脲酶、蔗糖酶、中性磷酸酶)活性间的关系。结果表明:在砂姜黑土中,残留态Cu、Cd、Zn在总量中所占比例很高,交换态、有机态、碳酸盐结合态含量明显低于残留态。在三种元素中,Zn的化学形态变化趋势最为一致,表现为残留态>碳酸盐结合态>铁锰结合态>有机态>交换态;砂姜黑土中交换态Cu、Cd、Zn对脲酶活性有显著抑制作用,有机态Cu、Cd、Zn对过氧化氢酶表现为一定程度的促进作用。因此,在砂姜黑土壤中,把交换态Cu、Cd、Zn和脲酶以及中性磷酸酶的活性共同作为评价土壤Cu、Cd、Zn污染程度的主要生化指标是可行的。     

钝化剂对铅锌尾矿砂中重金属的固化作用

铅锌尾矿砂重金属含量高,对环境危害大。为了减缓铅锌尾矿砂的重金属污染风险,采用室内培养实验方法,在铅锌尾矿砂中添加油菜秸秆、芒草秸秆、水稻秸秆、石灰和磷酸一铵等钝化剂,并通过DTPA及Tessier连续提取铅、锌、镉的化学形态,评价钝化剂对铅、锌、镉的移动性和生物有效性的影响。结果表明,油菜秸秆、芒草秸秆、水稻秸秆、石灰和磷酸一铵均显著地降低Cd的生物有效性及其迁移能力;磷酸一铵、油菜秸秆均能有效地降低尾矿砂中Pb的生物有效性及其迁移能力,尤其是磷酸一铵有极显著的效果;油菜秸秆、芒草秸秆、水稻秸秆和磷酸一铵均能有效地降低尾矿砂中Zn的生物有效性及其迁移能力。尾矿砂中DTPA态Cd、Zn与交换态、碳酸盐结合态Cd、Zn极显著正相关,DTPA态Pb与碳酸盐结合态Pb极显著正相关。从Pb、Cd、Zn生物有效态含量的减少方面考虑,油菜秸秆和磷酸一铵是较好的铅锌尾矿砂原位钝化剂。     

不同钝化剂对铜污染土壤原位钝化修复

考察了磷酸二氢钾、碳酸钙、硅酸钠、自制草木灰和自制生物质炭5种钝化剂对Cu污染土壤的钝化修复效果,对修复后的土壤进行了X射线衍射(XRD)分析;同时,对欧共体标准物质局提出的三步提取法(简称BCR法)进行了适当的改进,并运用改进的BCR法对Cu在土壤中的形态进行分析,以探讨不同钝化剂的作用机理。结果表明,5种钝化剂的投加量分别为50、100、20、20和20 g/kg时,对土壤钝化修复效果最佳,投加钝化剂后,土壤中可交换态Cu含量快速减少、残渣态Cu含量快速增加。其中,自制草木灰由于提高土壤p H更易与Cu生成沉淀,对Cu的钝化效果最佳,该钝化剂使有效态Cu含量减少53%,可交换态Cu含量减少49.2%,残渣态Cu含量增加4.7倍,有效地降低了Cu的生物毒性。     

基于同位素标记和连续提取法研究磷基材料对土壤铅的钝化行为

通过同位素标记手段,并结合Tessier连续提取法,研究贝壳粉、磷酸氢二铵、羟基磷灰石以及这3种磷基材料的复合钝化剂对土壤Pb的钝化行为及其作用机理。结果发现,土壤中所有Pb形态都可被外加的富集206Pb同位素标记,但其中残渣态Pb较难与富集同位素交换,表明残渣态Pb在土壤中稳定性较强。添加磷基钝化剂(除羟基磷灰石外)后,土壤pH值均显著提高(P<0.05)。所有钝化剂能使土壤有机质含量和阳离子交换量显著升高(P<0.05)。通过对206Pb的监测,发现磷基钝化剂对水溶态(磷酸氢二铵除外)、可交换态、碳酸盐结合态和铁锰氧化物结合态Pb均有显著的钝化作用(P<0.05),其中复合钝化剂和磷酸氢二铵对可交换态Pb的钝化率可分别达到93.3%和89.7%,且磷基钝化剂可导致有机质结合态和残渣态中Pb的含量显著升高(P<0.05)。此外,通过Visual MINTEQ模型计算表明,复合钝化剂和磷酸氢二铵可通过产生氯磷酸盐等4种铅磷酸盐而有效降低土壤Pb2+的活度,达到钝化的效果。     

不同钝化剂组合对土壤铬铜赋存形态及在水稻中积累的影响

为了筛选出能有效抑制水稻各部位吸收积累Cr和Cu的有机和无机材料钝化剂组合,选取水稻土以盆栽试验研究了15种钝化剂组合对土壤Cr和Cu赋存形态及水稻各部位吸收积累Cr和Cu的影响。结果表明:15种钝化剂组合施用使土壤pH上升0.25～1.04,土壤阳离子交换量增加2.65%～50.96%,土壤有机质含量增加0.22%～17.20%,土壤可交换态Cr含量降低35.21%～55.63%;除生石灰+钝化剂4+鸡粪组合使土壤可还原态显著增加外,其他组合的土壤可还原态Cr无显著变化;土壤可氧化态和残渣态Cr均无明显变化;土壤可交换态Cu含量降低6.66%～33.42%;土壤可还原态和可氧化态Cu无明显变化;土壤残渣态Cu增加0.32%～5.04%,其中钝化剂3、生石灰+钝化剂1+鸡粪、生石灰+钝化剂4+鸡粪3个组合能显著增加土壤残渣态含量。根系对Cr和Cu的富集能力最大,15种钝化剂组合可使水稻根系、秸秆、稻壳和糙米中Cr含量分别下降4.59%～49.41%,39.84%～76.87%,7.14%～31.60%,17.32%～67.10%,水稻根系、秸秆、稻壳和糙米中Cu含量分别下降10.57%～48.41%,7.99%～52.53%,21.12%～45.11%,14.39%～66.92%。15种钝化剂组合均可降低糙米中Cr和Cu的含量,其中以生石灰+钝化剂2+鸡粪的效果最佳。     

纳米羟基磷灰石对重金属污染土壤Cu/Cd形态分布及土壤酶活性影响

通过室内培养实验,研究了纳米羟基磷灰石对重金属污染土壤Cu/Cd形态分布及土壤酶活性的影响。结果表明,施加纳米羟基磷灰石显著提高了土壤pH,其中3%和5%添加剂量处理60 d后使土壤pH分别提高了1.23个和1.35个单位;纳米羟基磷灰石显著减少了毒性较强的离子交换态Cu/Cd的含量,增加了毒性中等的碳酸盐结合态、铁锰氧化物结合态、有机结合态及毒性最低的残留态Cu/Cd含量,使Cu/Cd由植物可利用态向潜在可利用态转变;纳米羟基磷灰石不同程度地提高了土壤过氧化氢酶、脲酶和酸性磷酸酶活性。3种酶活性与Cu/Cd形态分布的相关性表明,过氧化氢酶和酸性磷酸酶对土壤重金属Cu/Cd活性变化比较敏感,可以作为重金属Cu/Cd污染土壤的评价指标。     

不同有机肥中Cu、 Zn在农田土壤中的有效性与形态归趋

【目的】畜禽粪便有机肥的施用是造成我国农田土壤重金属污染的重要原因之一。本文选用两种典型规模化养殖场畜禽粪便有机肥,研究其在石灰性土壤和酸性土壤上施用1年后Cu、 Zn的有效性和形态归趋,为客观评价畜禽粪便有机肥中重金属进入土壤后的环境行为和生态风险提供理论依据。【方法】采用温室土壤培养试验,在石灰性土壤和酸性土壤上分别设对照(CK)、 施2%鸡粪(CM2%)、 施5%鸡粪(CM5%)、 施与CM2%、 CM5%含等量Cu、 Zn的重金属无机盐溶液(CS2%、 CS5%)、 施2%猪粪(PM2%)、 施5%猪粪(PM5%)、 施与PM2%、 PM5%含等量Cu、 Zn的重金属无机盐溶液(PS2%、 PS5%)9个处理,每个处理设3次重复,在温室条件下培养1年。测定土壤pH值, EDTA提取有效态Cu、 Zn以及采用改进Tessier连续提取法提取的各形态Cu、 Zn的含量,分析鸡粪、 猪粪及等量无机盐溶液中Cu、 Zn进入土壤后的有效性和形态归趋。【结果】施用鸡粪和猪粪1年后,石灰性土壤的pH值降低,酸性土壤的pH值升高,施用5%猪粪时石灰性土壤pH值降低了0.23个单位,酸性土壤pH值升高了0.87个单位。施入鸡粪、 猪粪1年后,石灰性土壤中有效态Zn和酸性土壤中有效态Cu、 Zn含量显著增加,施用5%猪粪时酸性土壤中有效态Cu含量增加了1.95倍,施用5%鸡粪时2种土壤中有效态Cu的含量均显著低于等量无机盐。施用鸡粪和等量无机盐后,2种土壤中交换态和有机结合态Cu的含量显著增加,交换态、 碳酸盐结合态、 有机结合态和铁锰氧化物结合态Zn的含量显著增加; 施用猪粪和等量无机盐后,2种土壤中交换态、 铁锰氧化物结合态和有机结合态Cu的含量显著增加,碳酸盐结合态和铁锰氧化物结合态Zn的含量显著增加。【结论】施用鸡粪、 猪粪提高了石灰性土壤中Zn和酸性土壤中Cu、 Zn的有效性,高用量条件下鸡粪中Cu的有效性低于等量无机盐。1年后, 通过畜禽粪便有机肥带入2种土壤中的Cu 主要以交换态和有机结合态的形式存在,Zn则主要以碳酸盐结合态、 铁锰氧化物结合态和有机结合态的形式存在。2种土壤上有机肥带入的Cu、 Zn转化为铁锰氧化物结合态的比例低于等量无机盐,2种有机肥带入2种土壤中的Cu转化为交换态和有机结合态的比例高于等量无机盐。鸡粪带入的Zn转化为交换态的比例在酸性土壤中低于等量无机盐,但在石灰性土壤中则高于等量无机盐。     

安徽主要水稻土中重金属形态分布与土壤酶活性研究

通过野外调查和实验分析,对安徽几类不同地貌下的水稻土中重金属Cu、Zn、Pb的化学形态特征及其与4种土壤酶活性间的关系进行了研究.结果表明:3种不同地区水稻土中,残留态和有机态Cu、Zn、Pb含量在总量中所占比例最高.平原和丘陵地区水稻土中有机结合态Cu、Zn、Pb明显高于山区;而山区水稻土中Fe-Mn氧化物结合态Cu、Zn、Pb相对含量高于平原和丘陵地区.在水稻土中,碳酸盐结合态Cu、Zn对过氧化氢酶活性的抑制作用最大,交换态Pb对脲酶活性的抑制作用最大.反映水稻土Cu、Zn污染用碳酸盐结合态Cu、Zn和过氧化氢酶活性指标,而反映Pb污染用交换态Pb和脲酶活性指标是可行的.     

粉煤灰对污染土壤中铜镉的稳定化

采用批衡量吸附和室内培养实验,考察了粉煤灰对Cu和Cd的吸附等温线及0.2%、0.5%、1%和2%用量的粉煤灰对土壤pH、有效态Cu和Cd、以及5种化学形态Cu和Cd分布的影响。结果表明:粉煤灰对Cu和Cd的吸附等温线均可以用Langmuir和Freundlich方程进行拟合,其对Cu的最大吸附量(9.90 mg/g)高于对Cd的最大吸附量(9.43 mg/g)。随着粉煤灰用量的增加,土壤pH显著增加,有效态Cu和Cd显著降低。同时,粉煤灰处理显著降低了离子交换态Cu和Cd含量,增加了铁锰氧化物结合态Cu和Cd含量,降低了Cu和Cd活性,使活性态Cu和Cd逐渐向潜在活性态和非活性态转化。其中培养60天后,2%处理的粉煤灰处理较对照pH提高了0.44个单位,离子交换态Cu和Cd分别降低了35.7%和35.9%。因此,粉煤灰能够有效吸附Cu和Cd,显著降低土壤有效态和离子交换态Cu和Cd的含量,在重金属稳定化修复应用中具有较好的应用前景。     

Reducing Bioavailability and Leachability of Copper in Soils using Coal Fly Ash,Apatite, and Bentonite

Soils treated with two concentrations of copper (Cu; 200 and 400 mg kg^?1) were amended with three amendments (coal fly ash, apatite, and bentonite) at the rates of 1.5% and 2.5%, respectively. The effects of amendment application on the bioavailability and leachability of Cu in the soil were evaluated using the wheat uptake, single extraction, and sequential extraction tests. The addition of coal fly ash, apatite, and bentonite at the rate of 2.5% increased wheat biomass by 50.5%, 41.1%, and 61.7%, respectively. The application of amendments significantly (P < 0.01) reduced the Cu contents extract that will buy DW (deionized water), TCLP (toxicity characteristics leaching procedure), and DTPA (diethylenetriaminepentaacetic acid) in the soil. The amendments also reduced the water-soluble/exchangeable, carbonate, iron (Fe)–manganese (Mn) oxide, and organically bound fraction contents of Cu but increased the amounts of residual Cu in soil. Our results demonstrated that these amendments were effective in reducing the bioavailability and leachability of Cu in soil.     

3种改良剂对油菜生物量及其吸收重金属的影响

通过连续三季盆栽试验研究粉煤灰、膨润土、腐殖酸提高油菜生物量,降低油菜Cd、Pb、Cu、Zn浓度的效果。结果表明,膨润土、腐殖酸、粉煤灰的施入提高油菜生物量的效果第二季好于第一、三季。仅考虑对生物量的影响,改良剂效果为膨润土>腐殖酸>粉煤灰。第二季膨润土降低油菜Cd浓度效果较好;第二季粉煤灰、第二季膨润土及第二、三季腐殖酸降低油菜Pb浓度效果较好,3种改良剂均有降低油菜中Pb浓度的效果;3种改良剂均未显著影响油菜中Cu浓度;第二季膨润土降低油菜Zn浓度效果较好。3种改良剂抑制土壤重金属进入油菜的效果不同,应用时可根据改良剂特点适时施入土壤,充分发挥改良剂吸附、固定重金属的作用。     

粉煤灰堆场附近农田土壤硒环境污染评价

对贞观山煤灰库附近农田土壤、土壤剖面、灌溉水、母岩以及稻米,蔬菜等农作物中Se含量特征及污染现状进行了系统分析与评价.结果显示:煤灰库周围的农田土壤Se含量范围为0.15～6.12mg/kg,受到不同程度污染.土壤Se含量空间分布特征表明.离煤灰库越近的农田土壤Se污染越严重.农田土壤Se污染主要是由Se含量超标地表水灌溉以及煤灰库的长期处置所引起的,受母岩的影响不大.研究区稻米Se含量较高,为0.04～1.12mg/kg,部分稻米样品Se含量超标严重,并且受土壤Se污染影响明显.长期食用Se含量超标大米对人体健康会产生潜在危害.     

Effects of Bentonite, Hydrogel and Biochar Amendments on Soil Hydraulic Properties from Saturation to Oven Dryness

Effects of hydrogel, bentonite, and biochar as soil amendments on soil hydraulic properties and improving water availability from saturation to oven dryness were investigated. Soils were mixed with hydrogel (0.10%, 0.25%, and 0.50%), bentonite (0.5%, 1.0%, and 2.5%), and biochar (1.0%, 2.5%, and 5.0%) as soil amendments (weight:weight). Three methods (extended multistep outflow (XMSO), evaporation (EVA), and WP4 dewpoint potentiometer) were used to measure soil hydraulic properties from saturation to oven dryness. The cumulative XMSO results were more uniform across all the applied pressure steps for the amended soils. The EVA exhibited a shorter linear decrease during the first evaporation stage and a lower evaporation rate during the second evaporation stage. The WP4 results also exhibited that soil amendments increased the soil water content of the amended soils at low matric potentials. The results of soil water retention curves revealed that the unamended soil retained less water at any matric potential compared to the amended soils. Soil hydraulic conductivity decreased with increasing amount of soil amendments. The saturated hydraulic conductivity was higher for the unamended soil than the soils amended with 2.5% bentonite, 0.50% hydrogel, and 5.0% biochar by 11, 3, and 18 times, respectively. These results suggested that soil amendments improved soil water retentivity, which confirmed the appropriateness of these soil amendments for potential use in sandy soil improvements. However, field experiments and economical perception studies should be considered for further investigation.     

Evaluation of fly ash as a soil amendment for the Atlantic Coastal Plain: I. Soil hydraulic properties and elemental leaching

A major limitation to crop yields in the Atlantic Coastal Plain is drought stress caused by the low moisture-holding capacities of the coarse-textured soils common to the area. Because coal fly ash is comprised primarily of silt and clay-sized particles, it has the potential, if applied at high enough rates, to permanently change soil texture and increase moisture holding capacity. A series of soil column studies were conducted to evaluate the effects of high rates of fly ash on soil hydraulic properties and elemental leaching of trace metals and boron. Fly ash from two Delaware power plants (EM=Edgemoor and IR=Indian River) was incorporated in a Hammonton loamy sand (fine-loamy, siliceous, mesic, Typic Hapludults) at six rates (0, 5, 10, 20, 30, and 40%, by weight). The effect of fly ash on soil moisture holding capacity, hydraulic conductivity, and wetting front velocity was determined. Leachates from columns amended with 30% fly ash were analyzed for B, Cd, Ni, Pb, Cu, and Zn. Soil moisture holding capacity was increased from 12% in the soil alone to 25% in the soil amended with 30% fly ash. Boron and soluble salts leached rapidly from ash amended soils while only trace quantities of Cd, Ni, Pb, Cu, and Zn were detected in column leachates.     

Enzyme Activities in a Sandy Soil Amended with Sewage Sludge and Coal Fly Ash

Previous studies showed that coal fly ash could stabilize sewage sludge by reducing metal availability, but fly ash may cause an adverse effect on soil microbial activities. Therefore, an experiment was performed to evaluate the effects of amendment of soil with anaerobically digested dewatered sewage sludge, stabilised with alkaline coal fly ash, on soil enzyme activity and the implications for soil nutrient cycling. Sewage sludge was amended with 0, 5, 10, 35 and 50% w/w of fly ash, and then the ash-sludge mixtures were incubated with a sandy soil at 1:1 (v/v). Dehydrogenase activity decreased with an increase in fly ash amendment level and the time of incubation. Soil receiving 5% ash-sludge amendment had a higher dehydrogenase activity than other treatments. Soil receiving 10% ash-sludge mixture had the highest urease activity and in general, urease activity decreased with increasing incubation time. Phosphatase activity was the highest at 5% ash-sludge mixture amended soil and no general trend was observed with time. Water-soluble Zn, Mn and Cu contents were suppressed by the addition of fly ash. The present experiment indicated that addition of 10% ash-sludge mixture should have a positive benefit on the activity of soil microorganisms, N and P nutrient cycling, and reduce the availability of heavy metals.     

Evaluation of Cocomposted Coal Fly Ash on Dynamics of Microbial Populations and Heavy Metal Uptake

Vicia faba, in a pot experiment with sandy and clayey soils under greenhouse conditions, was checked for growth response to different amendments with coal alkaline fly ash or cocomposted fly ash mixed with lignocellulosic residues. Soil microbial populations, pH and electrical conductivity as well as heavy metal uptake by plants were monitored. At rates of five and ten percent (on a dry matter basis) in both soils, neither fly ash alone nor cocomposted fly ash exerted any negative effect. Plant biomass production was not influenced in either clayey or sandy soil. Alkaline fly ash did not promote microbial growth when applied alone to the soils. However, cocomposted fly ash generally increased bacterial and actinomycetes counts in both soils. Fungi were not affected by ash. Due to the increase of soil pH by alkaline fly ash or cocomposted fly ash, plant uptake of heavy metals was depressed in the sandy soil. Heavy metal mobility did not cause change in the clayey soil where a high buffering capacity mitigated the effects of fly ash amendments.     

Phosphorus adsorption and desorption in a sandy soil amended with high rates of coal fly ash

Abstract

Amending sandy, drought‐prone soils with high rates of coal fly ash has the potential to improve plant growth by enhancing soil moisture relations. However, some studies have questioned the plant availability of native and fertilizer phosphorus (P) in ash‐amended soils. We used a batch adsorption study and a 42 day incubation study to examine the effects of amending an Evesboro loamy sand with fly ash (0–30%, w:w) on P availability and adsorption‐desorption. Fly ash increased soil test P from 13 mg/kg (soil) to 34 mg/kg (30% ash) but had little effect on readily desorbable P. The adsorption or desorption of P was not markedly influenced by fly ash in either batch or incubation studies except at the highest ash and P rates. In the batch study, the greatest increases in P adsorption were seen at the 20% and 30% ash rates and P equilibium concentrations >20 mg/L. Immediate and long‐term decreases in P desorption occurred in the incubation study at all ash rates when ≥500 mg P/kg were added but fly ash had little effect on P desorption at P rates ≤250 mg P/kg.     

氧化节杆菌生物降解苯并芘

A pot experiment was conducted with multi-metal (Pb, Cd, Cu, and Zn) contaminated acidic soil to investigate changes in available metal burden resulting from the application of industrial wastes (fly ash and steel slag). The efficiency of amendments-induced metal stabilization was evaluated by diffusive gradients in thin films (DGT), sequential extraction, and plant uptake. The stability of remediation was assessed by an acidification test and by chemical equilibrium modeling. Addition of fly ash (20 g kg-1 ) and steel slag (3 g kg-1 ) resulted in similar increase in soil pH. Both amendments significantly decreased the concentrations of metals measured with DGT (C DGT) and the metal uptake by Oryza sativa L. Significant correlations were found between C DGT and the concentration of a combination of metal fractions (exchangeable, bound to carbonates, and bound to Fe/Mn oxides), unraveling the labile species that participate in the flux of metal resupply. The capability of metal resupply, as reflected by the R (ratio of C DGT to pore water metal concentration) values, significantly decreased in the amended soils. The C DGT correlated well with the plant uptake, suggesting that DGT is a good indicator for bioavailability. Acidification raised the extractable metal concentration in amended soil but the concentration did not return to the pre-amendment level. Equilibrium modeling indicated that the soil amendments induced the precipitation of several Fe, Al and Ca minerals, which may play a positive role in metal stabilization. Chemical stabilization with alkaline amendments could be an effective and stable soil remediation strategy for attenuating metal bioavailability and reducing plant metal uptake.