CPC/CaO_2氧缓释复合材料的制备及其释氧性能探讨

利用过氧化钙(CaO2)遇水释放氧气的特性,采用混合法将CaO2载入到磷酸钙骨水泥(CPC)中,并通过挤出-滚圆造粒方法制备出CPC/CaO2氧缓释复合材料,旨在为污染地下水的好氧生物修复技术提供一种长期、高效的供氧源。由X射线衍射(XRD)分析可知,通过固相反应制取的CPC主要成分为Ca5(PO4)3(OH)和Ca10(PO4)6(OH)2,具有较快的固化时间和固化效果;CPC/CaO2氧缓释复合材料分3个阶段进行释氧,其中2、3阶段分别符合一级和零级释氧动力学特征,且其释氧速率和释氧周期得到明显改善。本研究成果可用于实际地下水修复工程,解决污染地下水原位生物修复过程中溶解氧(DO)的输送问题。     

地下水PRB原位生物修复中一种释氧材料的改进技术及效果分析

释氧材料经济有效的释氧是地下水原位生物修复的关键因素。实验通过在释氧材料中加入膨润土、磷酸二氢钾和硫酸铵等,改进释氧材料的性能。柱实验结果显示,该释氧材料释氧速率缓慢,释氧时间长,可以使溶液中DO长期保持在5 mg/L以上;另外,释氧材料中添加的缓冲剂及天然含水层介质对pH值有较好的缓冲作用,可以使pH值达到后续生物修复的要求。     

CPC/CaO2氧缓释复合材料的制备及其释氧性能探讨

利用过氧化钙（CaO2）遇水释放氧气的特性,采用混合法将CaO2载入到磷酸钙骨水泥（CPC）中,并通过挤出-滚圆造粒方法制备出CPC/CaO2氧缓释复合材料,旨在为污染地下水的好氧生物修复技术提供一种长期、高效的供氧源。由X射线衍射（XRD）分析可知,通过固相反应制取的CPC主要成分为Ca5（PO4）3（OH）和Ca10（PO4）6（OH）2,具有较快的固化时间和固化效果;CPC/CaO2氧缓释复合材料分3个阶段进行释氧,其中2、3阶段分别符合一级和零级释氧动力学特征,且其释氧速率和释氧周期得到明显改善。本研究成果可用于实际地下水修复工程,解决污染地下水原位生物修复过程中溶解氧（DO）的输送问题。     

新型释氧材料制备及对湿地堵塞解除研究

针对人工湿地内部DO含量较低引起的生物性堵塞,污水处理效率下降的问题,采用投加释氧材料的方法来提高湿地内部DO含量,修复生物性堵塞。采用CaO_2为释氧剂制备释氧材料,进行释氧性能研究。结果表明:采用大孔弱酸性丙烯酸系阳离子交换树脂作为包埋剂制成的释氧材料释氧性能最佳。在模拟人工湿地污水系统中,释氧材料可使反应器中DO质量浓度在15d内保持在5.0mg/L以上,并且pH保持中性水平,相较未投加释氧材料的对照组,30d内COD的平均降解效率提高125%。投加释氧材料可以使发生生物性堵塞的人工湿地系统在连续运行条件下基质孔隙率在15d内恢复到初始水平的83%左右,并且相较机械曝气具有操作便捷、不受环境限制以及成本低廉的优点。     

铁铝盐基离子对土壤中水溶性氟环境效应的影响

氧化物或粘土矿物可吸附氟离子,但磷酸根离子与氟离子存在竞争吸附效应,造成氟的环境存在量、存在形态及生物效应更加复杂,影响了环境中氟污染的治理.试验选用典型贵州黄壤和石灰土,通过向模拟高氟污染土壤中添加铁铝盐基离子和磷酸盐,采用两因素最优设计,研究外源物质对土壤中水溶性氟的影响.结果表明,FeCl3·6H2O或AlCl3·6H2O都能降低土壤中水溶性氟,而KH2PO4使土壤中水溶性氟增加,对黄壤和石灰土中水溶性氟影响效果大小依次为FeCl3·6H2O(AlCl3·6H2O)、KH2PO4.同时表明,采用铁铝盐基离子改变黄壤性质,达到降氟效果仍有很大潜力,而石灰土环境在高添加铁铝盐基离子水平下继续添加FeCl3·6H2O或AlCl3·6H2O降低土壤中水溶性氟的作用较弱.从土壤pH看,黄壤水溶性氟受试验因子影响复杂,土壤pH低水溶性氟不一定低,pH在4～6时,氟元素的形态及有效性尤其复杂,而石灰土中水溶性氟基本随pH降低而降低.     

阳极pH对Fe(Ⅲ)强化阴极电动修复Pb污染土壤的影响

土壤的pH值对电动力修复技术至关重要。利用Fe(NO3)3作为阴极电解液,不仅可以消耗电解产生的OH-,不会对土壤造成二次污染,并且修复后土壤的pH相对较低。在土壤室和阴极室之间添加活性炭纤维和阳离子膜,增强修复效果。采用配制的Pb污染土壤,在电场强度为1 V·cm-1的条件下进行实验,研究不同pH(3、4、5)的柠檬酸-柠檬酸钠阳极电解液对电动力学修复Pb污染土壤效果的影响。结果表明:在利用Fe(Ⅲ)-活性炭纤维强化电动修复时,添加的阳极电解液pH值越小,Pb的去除效果越好;各阳极电解液pH值递增梯度相对应Pb的截面最大去除率分别为:80.53%、53.1%和40.69%。通过分析残留在土壤中Pb的重金属形态,得到在距离阳极4 cm处的土壤截面中Pb主要以较稳定的、环境毒性较低的有机态和残渣态存在。     

造纸白泥和粉煤灰的添加对污泥消化液中氮磷回收的影响

污泥厌氧消化液中含有丰富的氮磷，若直接排放到环境中，将会对附近水体造成严重污染。由于消化液中Mg^2＋和Ca^2＋的含量很低，严重影响了氮磷的回收效果。把造纸白泥和粉煤灰引入到污泥厌氧消化液氮磷的回收当中，可以明显地提升消化液pH和提高PO4^3-P和NH3-N回收率。实验结果表明：当造纸白泥添加量为4g／（L·h）时，曝气12h后，pH可达10．19，此时PO4^3-P和NH3-N回收率分别达到64％和45％；而当粉煤灰添加量为4g／（L·h）时，曝气12h后，pH达到9．63，PO4^3-P和NH3-N回收率分别为46％和41％。但仅用曝气方式处理，12h后，pH值仅为8．52，PO4^3-P和NH3-N回收率分别只有20％和18％。实验结果还表明，水力停留时间（HRT）越大，pH上升速度越快，幅度越大，氮磷的回收效果就越好。     

实时控制SBR系统中的短程硝化反硝化

以人工模拟高氨氮废水为研究对象,采用循环间歇式曝气方式,以溶解氧浓度(DO)和pH值为过程控制参数,对SBR系统进行实时控制、全程跟踪.根据此过程中COD、NH4 -N、NO2--N和NO3--N 4项水质指标的变化情况,研究SBR系统中的短程硝化反硝化工艺.实验结果表明,在短程硝化反硝化工艺中,采用较高曝气量,并且在曝气过程中用DO和pH值作为过程控制参数是可行的.     

磷酸铵镁法回收污泥浓缩液中氮磷的影响因素研究

以生物除磷脱氮污水处理厂污泥浓缩液为研究对象,采用正交实验方法,通过测定溶解性磷和NH4+-N的变化探索pH值、[Mg2+]/[PO34-]和[NH4+]/[PO43-]对MAP法回收氮磷效率的影响。研究表明,pH值是影响氮磷回收的一个最重要因素,当pH值达到10时,磷回收率达到最大值(81.9%),当pH值由9上升到11时,氮的去除率随pH值的升高而增加;[Mg2+]/[PO43-]和[NH4+]/[PO43-]都会影响鸟粪石(MAP)法对磷的回收率,比值越大,磷回收率越高,但当比值达到一定值后,磷回收率增长幅度趋于减缓,仅考虑磷的回收效率,[Mg2+]/[PO43-]和[NH4+]/[PO43-]的最优配比分别为1.4和6;氮去除率也受镁磷比和氮磷比的影响,当[Mg2+]/[PO43-]为1.3时,氮去除率最高,而当[NH4+]/[PO43-]为4~8时,氮去除率随着氮磷比的升高而逐渐降低。     

纳米铁原位注入技术对六价铬污染地下水的修复

纳米零价铁原位注入是六价铬污染地下水的有效修复技术之一。为验证其场地修复效果,在北京某电镀厂搬迁后的遗留六价铬污染场地,现场制备纳米铁并通过原位注入对场地内六价铬污染地下水进行原位修复现场中试研究。选取6 m×6 m实验场地,在地下水中六价铬污染浓度最高为2 mg·L~(-1)的中心点设置注射井并在四周设置4口监测井。实验结果表明,原位注入纳米铁药剂具有良好修复效果,修复后该实验场地范围内地下水中六价铬浓度均低于地下水质量Ⅳ类标准0.1 mg·L~(-1),注射井中六价铬还原率达到99%。通过对注射井及监测井地下水中pH、溶解氧、氧化还原电位等检测指标进行跟踪监测和相关性分析,发现氧化还原电位与污染物浓度变化相关性最强,可以作为污染物变化的表征因子。该中试研究结果对于六价铬污染地下水的原位修复具有重要的参考价值。     

载铁活化天然沸石处理高氟地下水

采用氯化铁改性天然沸石进行地下水除氟效果的研究,考察了地下水中4种阴离子Cl-、HCO3-、SO24-和PO34-对该改性沸石除氟效果的影响,并分析了其除氟机理和表面成分。研究结果表明,对于初始氟浓度不同的水样,随着阴离子浓度的增加,吸附剂对氟的去除率逐渐下降。Cl-对吸附剂除氟效果影响较小,氟去除率降低较慢;随着HCO3-浓度的增大(由100 mg/L到1 000 mg/L),水样pH由8.42缓慢升高到9.52,而氟去除率则由70.36%缓慢下降到56.73%(2mg/L);SO24-及PO34-对改性沸石除氟效果影响较大,氟去除率降低较快,且PO34-的影响大于SO24-。可以得到载铁活化天然沸石对4种阴离子的吸附顺序为:PO34->SO24->HCO3->Cl-。     

Geochemistry of a septic-system plume in a coastal barrier bar, Point Pelee, Ontario, Canada

The major ion and trace metal geochemistry of a septic system plume in a shallow sand aquifer was characterized to assess geochemical processes controlling the transport of nutrients and their release to a nearby wetland. The plume was generated from a 16-year-old tile bed, and is more than 60 m long, 40 m wide and 7 m thick. The groundwater pH at the site is near neutral, but up to 0.4 units lower in the plume core as a result of H⁺ generated from NH₃ and DOC oxidation in the unsaturated zone. The plume can be divided into distinct redox zones, which show differences in nutrient mobility. Proximal to the tile bed, there is a shallow suboxic zone, with intermediate Eh values (>400 mV), low concentrations of dissolved oxygen (<1.0 mg/l), and elevated concentrations of Mn (1–3 mg/l) and nutrients (10–80 mg/l NO₃–N, 1–15 mg/l NH₃–N, 0.1–1.5 mg/l PO₄–P, 6–13 mg/l dissolved organic carbon). At the base of the aquifer, there is a reduced zone (Eh<200 mV) with elevated concentrations of Fe (1–14 mg/l), PO₄ and NH₃, but negligible concentrations of NO₃ (<0.01 mg/l N). Distal from the tile bed, the shallow groundwater is suboxic to oxic, and has elevated concentrations of NO₃ and NH_3, but negligible PO₄. In the lower reduced zone, elevated concentrations of PO₄ occur up to 60 m away. The release of groundwater containing even very low concentrations of PO₄ (<0.02 mg/l P) can lead to the development of eutrophic conditions in surface water bodies. Geochemical calculations indicate that, in the Mn-rich zone, the groundwater is close to saturation or supersaturated with respect to hydroxyapatite, rhodochrosite, calcite and ferrihydrite. In the reduced zone, the groundwater is close to saturation or supersaturated with respect to hydroxyapatite, vivianite, calcite and siderite. Formation of these phases, or related phases, are likely limiting the concentrations of dissolved PO₄, Fe and Mn and controlling the geochemical evolution of the plume.     

电增强载铝活性炭纤维吸附除氟的效果与影响因素

以含氟地下水为研究对象,采用自制电促吸附除氟反应器,开展电增强载铝活性炭纤维吸附除氟的动态实验,研究了不同电压、极板间距、地下水碱度和流速对吸附除氟效果的影响。实验结果表明,在负载炭纤维毡的电极一端加正电,可以提高除氟效果。当电压为1.6 V时除氟效果较好,单位面积炭毡处理达标水量为56.7 L/m2;极板间距设置为4mm时电吸附反应器除氟效果最佳;通过调节pH改变地下水碱度,当地下水pH调节为5.5时,电吸附反应器除氟效果较未调节前提高50%;当采用3对电极板,流速为1.88 m/h时,达到最高表面处理负荷2 073.6 L/(m2.d);探究了反应器的反洗再生方式,并连续进行了吸附再生的动态实验;穿透的反应器以Al2(SO4)3溶液为再生液并采用反向加电1.6 V的方式,可以达到较好的再生效果,实现连续动态运行。     

诱导结晶法去除地下水中氟离子简

针对现行高氟地下水处理工艺中存在的工艺复杂、运行管理困难等问题，提出采用诱导结晶法除氟。其技术核心是在高氟水中投加氟磷灰石作为晶种，并投加磷酸盐和钙盐使水中氟离子在晶种表面生成氟磷酸钙（Ca₁₀（PO₄） ₆F₂）结晶。通过单因素实验得出最佳工艺条件：投加8g/L氟磷灰石，并投加NaH₂PO₄和CaCl₂，使钙离子、磷酸根离子和氟离子的摩尔比为10：5：1，搅拌速度为100 r/min，反应时间1 h。反应中磷酸根离子和钙离子的利用率分别达到98%和25%以上。电子扫描显微镜（SEM）表征晶种在参与反应后，表面有结晶生成。研究表明，采用诱导结晶法可将水中氟离子浓度从5~10 mg/L降至1 mg/L以下，达到饮用水水质标准。     

Characterization of eco-cement paste produced from waste sludges

In this study, marble sludge, sewage sludge, drinking water treatment plant sludge, and basic oxygen furnace sludge were used as replacements for limestone, sand, clay, and iron slag, respectively, as the raw materials for the production of cement in order to produce eco-cement. It was found that it is feasible to use marble sludge to replace up to 50% of the limestone and also that other materials can serve as total replacements for the raw materials typically used in the production of cement. The major components of Portland cement were all found in eco-cement clinkers. The eco-cement was confirmed to produce calcium hydroxide and calcium silicate hydrates during the hydration process, increasing densification with the curing age. The compressive strength (S_c) and microstructural evaluations conducted at 28 d revealed the usefulness of eco-cement. It was observed that the S_c data correlated linearly with the pore volume (P) data at 28 d. The proposed model equation could be represented as S_c = 178-461P (correlation coefficient, R² = 0.96). Two parameters, the large capillary pore volume and the medium capillary pore volume, were evaluated using multiple regression analysis.     

固态碳源去除地下水硝酸盐的模拟实验

选取了5种研究较少的固体材料,棉花、丝瓜络、甘蔗渣、可降解餐盒、木屑作为去除地下水硝酸盐的外加碳源。在锥形瓶中进行反硝化对比实验,研究了不同固态碳源下NO3--N、NO2--N、NH4+-N及pH的变化情况,分析了NO3--N及总氮的去除率。研究结果表明,反硝化过程中pH呈升高趋势,在6.9～8.5范围内浮动。可降解餐盒和丝瓜络相对于其他的固态碳源来说,对NO3--N和总氮有较高的去除率,但丝瓜络的总氮去除率明显低于可降解餐盒。可降解餐盒的硝酸盐去除率达到98.28%,总氮去除率达到93.48%。可降解餐盒能够有效地去除地下水硝酸盐,达到以废治废的效果,是经济有效的最佳固态碳源。     

Influence of algal bloom degradation on nutrient release at the sediment–water interface in Lake Taihu, China

Algal bloom could drastically influence the nutrient cycling in lakes. To understand how the internal nutrient release responds to algal bloom decay, water and sediment columns were sampled at 22 sites from four distinct regions of China’s eutrophic Lake Taihu and incubated in the laboratory to examine the influence of massive algal bloom decay on nutrient release from sediment. The column experiment involved three treatments: (1) water and sediment (WS); (2) water and algal bloom (WA); and (3) water, sediment, and algal bloom (WSA). Concentrations of dissolved oxygen (DO), total nitrogen (TN), total phosphorus (TP), ammonium (NH ₄ ⁺ -N), and orthophosphate (PO ₄ ^3? -P) were recorded during incubation. The decay of algal material caused a more rapid decrease in DO than in the algae-free controls and led to significant increases in NH ₄ ⁺ -N and PO ₄ ^3? -P in the water. The presence of algae during the incubation had a regionally variable effect on sediment nutrient profiles. In the absence of decaying algae (treatment WS), sediment nutrient concentrations decreased during the incubation. In the presence of blooms (WSA), sediments from the river mouth released P to the overlying water, while sediments from other regions absorbed surplus P from the water. This experiment showed that large-scale algal decay will dramatically affect nutrient cycling at the sediment–water interface and would potentially transfer the function of sediment as “container” or “supplier” in Taihu, although oxygen exchange with atmosphere in lake water was stronger than in columns. The magnitude of the effect depends on the physical–chemical character of the sediments.     

Products and stability of phosphate reactions with lead under freeze-thaw cycling in simple systems

Orthophosphate fixation of metal contaminated soils in environments that undergo freeze-thaw cycles is understudied. Freeze-thaw cycling potentially influences the reaction rate, mineral chemical stability and physical breakdown of particles during fixation. This study determines what products form when phosphate (triple superphosphate [Ca(H₂PO₄)₂] or sodium phosphate [Na₃PO₄]) reacts with lead (PbSO₄ or PbCl₂) in simple chemical systems in vitro, and assesses potential changes in formation during freeze-thaw cycles. Systems were subjected to multiple freeze-thaw cycles from +10 °C to −20 °C and then analysed by X-ray diffractometry. Pyromorphite formed in all systems and was stable over multiple freeze-thaw cycles. Low temperature lead orthophosphate reaction efficiency varied according to both phosphate and lead source; the most time-efficient pyromorphite formation was observed when PbSO₄ and Na₃PO₄ were present together. These findings have implications for the manner in which metal contaminated materials in freezing ground can be treated with phosphate.     

Bioremediation of a diesel fuel contaminated aquifer: simulation studies in laboratory aquifer columns

The in situ bioremediation of aquifers contaminated with petroleum hydrocarbons is commonly based on the infiltration of groundwater supplemented with oxidants (e.g., O₂, NO₃⁻) and nutrients (e.g., NH₄⁺, PO₄³⁻). These additions stimulate the microbial activity in the aquifer and several field studies describing the resulting processes have been published. However, due to the heterogeneity of the subsurface and due to the limited number of observation wells usually available, these field data do not offer a sufficient spatial and temporal resolution. In this study, flow-through columns of 47-cm length equipped with 17 sampling ports were filled with homogeneously contaminated aquifer material from a diesel fuel contaminated in situ bioremediation site. The columns were operated over 96 days at 12°C with artificial groundwater supplemented with O₂, NO₃⁻ and PO₄³⁻. Concentration profiles of O₂, NO₃⁻, NO₂⁻, dissolved inorganic and organic carbon (DIC and DOC, respectively), protein, microbial cells and total residual hydrocarbons were measured. Within the first 12 cm, corresponding to a mean groundwater residence time of < 3.6 h, a steep O₂ decrease from 4.6 to < 0.3 mg l⁻¹, denitrification, a production of DIC and DOC, high microbial cell numbers and a high removal of hydrocarbons were observed. Within a distance of 24 to 40.5 cm from the infiltration, O₂ was below 0.1 mg l⁻¹ and a denitrifying activity was found. In the presence and in the absence of O₂, n-alkanes were preferentially degraded compared to branched alkanes. The results demonstrate that: (1) infiltration of aerobic groundwater into columns filled with aquifer material contaminated with hydrocarbons leads to a rapid depletion of O₂; (2) O₂ and NO₃⁻ can serve as oxidants for the mineralization of hydrocarbons; and (3) the modelling of redox processes in aquifers has to consider denitrifying activity in presence of O₂.