A Comparative Study of Pollutant Removal Stability in Hybrid Wetland Columns

This study investigated the effects of two alternative substrates(wood mulch and zeolite) on the performance of three laboratory-scale hybrid wetland systems that had identical system components and configurations.Each system consisted of a vertical flow(VF) wetland column,followed by a horizontal flow(HF) column and a vertical flow column.The substrates employed were wood mulch,gravel and zeolite,and Phragmites australis were planted in each column.The systems received synthetic wastewater,with pollutant loadings in the range of 8.5-38.0 g/(m2·d) total nitrogen(TN) and 4.0-46.4 g/(m2·d) biological oxygen demand(BOD5).Wood mulch and zeolite substrates showed higher efficiencies in terms of removing nitrogenous compounds and biodegradable organics.The supply of organic carbon from the organic mulch substrates enhanced denitrification,while adsorption of influent ammoniacal nitrogen(NH4-N) in zeolite played a major role in the removal of nitrogenous species in the wetland columns.Overall,the average percentage removals of TN and BOD5 reached >66% and >96% respectively,indicating stable performances by the hybrid wetland systems under the experimental loading ranges.Mathematical models were developed,based on the combination of Monod kinetics and continuously-stirred tank reactor(CSTR) flow patterns to describe the degradation of nitrogenous compounds.Predictions by the models closely matched the experimental data,indicating the validity and potential application of Monod kinetics in the modelling and design of treatment wetlands.     

Interplay between equilibrium and kinetics in prograde metamorphism of pelites: an example from the Nelson aureole, British Columbia

The distribution of metapelitic mineral assemblages in the Nelson aureole, British Columbia, generally conforms to what is predicted from phase equilibria. However, in detail, the sequence and spacing of isograds, mineral textures and mineral compositions and mineral chemical zoning do not. Two of the main disequilibrium features in the aureole are: (i) delay in the onset and progress of several reactions, i.e. overstepping in temperature; and (ii) unreactivity of staurolite and especially garnet porphyroblasts when they are reactants in prograde reactions. The thermal overstepping is ascribed to difficulty of nucleation of the product porphyroblasts and sluggishness of dissolution of porphyroblasts when they are reactants. The extent to which these kinetic barriers delay the onset of reaction is related to the reaction affinity of each reaction, defined herein as the Gibbs free‐energy difference between the thermodynamically stable, but not‐yet‐crystallized, products and the metastable reactants. For oversteps in temperature (ΔT), reaction affinity is, in turn, related to the difference in entropy (ΔS) between these two states through the relation A = ΔT * ΔS. Mineral reactions which release large quantities of H₂O, such as chlorite‐consuming reactions, have a higher entropy change per unit of temperature overstep, and therefore a higher reaction affinity, than those which release little or no H₂O, such as the chlorite‐free staurolite‐consuming reaction. Thermal overstepping is consequently expected to be less for the former than for the latter, as was estimated in the aureole where 0 to 30 °C overstepping was required for garnet, staurolite and andalusite growth from a muscovite + chlorite‐bearing precursor rock and ～70 °C overstepping was required for the growth of Al₂SiO₅ from a staurolite‐bearing, chlorite‐free precursor. In all cases, reaction progress was strongly influenced by the presence or absence of fluid, with presence of fluid lowering kinetic barriers to nucleation and growth and therefore the degree of thermal overstepping. Textural features of rocks from the nearly coincident garnet, staurolite and andalusite isograds are suggestive of a fluid‐catalysed ‘cascade effect’ in which reaction took place in a narrow temperature interval; several competing muscovite + chlorite‐consuming reactions, some metastable, appear to have occurred in parallel. Metamorphic reaction, fluid release and possibly fluid presence in general in the aureole were episodic rather than continuous, and in several cases well removed from equilibrium conditions. The extent to which these findings apply to regional metamorphism depends on several factors, a major one being enhanced deformation, which is expected to lower kinetic barriers to nucleation and growth.     

吐哈盆地低熟气评价的化学动力学方法及其应用

针对目前尚无公认的有效方法评价低熟气生成量的难题,本文从低熟气的（低温）热成因机理出发,认为被广泛、成功应用于成熟的热成因天然气生成量评价的化学动力学理论仍然应该是评价低熟气生成量的有效方法。在此基础上,建立并标定了吐哈盆地代表性泥岩、煤岩干酪根成气的化学动力学模型,与可能部分成为低熟气先质的非烃、沥青质的化学动力学模型一起,构成了评价低熟气生成量的方法。标定结果表明,盆地内有机质成气的平均活化能低于其成油的活化能,而且成气过程中低活化能组分的含量也高于成油过程。这可能正是吐哈盆地的有机质在大量生油之前的低成熟阶段,能开始规模性地生成低熟气、从而导致工业性的低熟气聚集的内因所在。应用表明,吐哈盆地低熟气的总生成量可观,达到632．15×10^11 m^3,而且生气强度较高,最高达到100×10^8m^3／km^2以上。吐哈盆地低熟气资源量约为3．16×10^11～12．62×10^11 m^3。可见,盆地内低熟气具有可观的勘探潜力。本文所建立的方法应该可被推广应用到其他含低熟气盆地的低熟气的评价当中。     

Solid phase characterization and metal deportment in a mussel shell bioreactor for the treatment of AMD,Stockton Coal Mine,New Zealand

The Stockton Coal Mine, located on the West Coast of New Zealand, is evaluating the use of a mussel shell bioreactor (MSB) to treat acidic metalliferous runoff from acid forming overburden. This novel approach is similar in concept to vertical flow wetlands (VFWs) and successive alkalinity producing systems (SAPS). The MSB system is a trapezoidal pit 2 m deep, 35 m long, 3–10 m wide with 60° angle sides. During operation it contained 160 tonnes (240 m³) of mussel shell material and was saturated with a 100–200 mm water cap. Influent flowed through the reactor at a mean rate of 0.3 L s⁻¹ resulting in a hydraulic retention time (HRT) of ≈6 days. The prototype MSB was in operation for a total of 1027 days, from June 2009 through March 2012, and effectively sequestered 99.7% of Al, 99.3% of Fe, 98.8% of Ni, 98.4% Tl and 99.3% of Zn, as determined from a previous evaluation of MSB performance. The MSB also effectively neutralized acidity, which resulted in an increase in influent pH from 2.8 to 6.9 in the effluent. Based on an examination of several excavated pits, five distinct reaction zones developed within the MSB. The reaction zones consisted of an allochthonous sediment layer (0–330 mm), an oxidized iron-rich ocherous layer (at 330–350 mm depth), an aluminum layer (at 350–600 mm depth) with geochemical variations throughout (350–500 mm and 500–600 mm); and a chemically reduced bottom shell layer (at 600–1100 mm). Representative samples were collected from each layer and analyzed using a combination of geochemical and physical methods to assess the stability of the secondary minerals and trace metal deportment within the MSB. Major elements Fe, Al, Ni, Tl, and Zn where preferentially associated with particular layers within the MSB. Elevated concentrations of Fe (110,000 mg kg⁻¹) were observed in the allochthonous sediment and ocherous precipitate layers, while Al (27,816 mg kg⁻¹), Ni (55 mg kg⁻¹), and Zn (655 mg kg⁻¹) were elevated within the aluminum and lower reduced depths within the MSB. Trace Tl (21 mg kg⁻¹) showed varying concentrations throughout the MSB, but was strongly correlated to lower layers of the system. Microbial biofilms were observed within the reduced portions of the shell layers often proximal to bacterial shaped sulfides. The geochemical assessment of the MSB presented in this study is the first of its kind for a MSB, and supports the argument that this system is another viable option for passive treatment of AMD.     

爱沙尼亚干酪根催化降解生烃过程及动力学研究

以爱沙尼亚油页岩干酪根为对象,利用热模拟实验方法和化工催化原理,考察了不同介质对干酪根热解生烃过程的影响,从热解生烃量、生烃组成特征及生烃动力学等方面进行了探讨。结果表明:膏岩对干酪根的生烃具有明显催化作用,碳酸盐岩对干酪根的生烃具有一定反催化作用,各种盐类对干酪根的生烃量影响较小。干酪根热解动力学研究表明,生烃动力学参数表观活化能E与视频率因子A两者之间不是独立变化的,而是具有一定的关系,即:E与lnA之间服从直线关系(R=0.99),这些认识对于深入探讨爱沙尼亚油页岩干酪根的化学结构、建立热解动力学模型具有一定的参考价值。     

Phosphate removal from water by naturally occurring shale,sandstone, and laterite: The role of iron oxides and of soluble species

Aqueous phosphate removal by three geomaterials from Ivory Coast was evaluated to determine their potential application as low-cost phosphate adsorbents in wastewater treatment. Batch experiments showed that phosphate uptake strongly depended on pH. Laterite and sandstone dissolution was less pronounced compared to shale. A correlation between concentrations of aqueous cation species released from shale and phosphate uptake was observed. The kinetics were well described using the pseudo-second-order model. Isotherms displayed a saturation level on shale, while phosphate uptake continuously increased for laterite and sandstone. The removal efficiency decreased in the following ranking order: laterite > sandstone > shale. Laterite was also the most efficient adsorbent in column experiments. The high phosphate removal efficiency of laterite (8.3 mg PO₄ g^?1) was attributed to the presence of superparamagnetic low grain sizes of goethite. Laterite is a particularly promising material for further investigation in wastewater treatment technology such as constructed wetlands.     

碳酸氢钠冷却结晶动力学

碳酸氢钠(NaHCO_3)俗称小苏打,其产品质量取决于颗粒的大小,晶体的形貌和样品的纯度等诸多因素。本论文基于连续稳态MSMPR结晶器原理,研究了不同停留时间下,碳酸氢钠从碳酸钠溶液中冷却结晶过程动力学。利用实验数据建立了NaHCO_3的结晶动力学操作模型。实验和计算结果表明,随停留时间的增加,NaHCO_3过饱和度降低,晶体生长速率和成核速率均减小,相应的平均粒径增加,细颗粒含量减小;适当延长停留时间是制取高品质小苏打产品的有效途径。冷却结晶过程可有效增加小苏打产量,小苏打收率维持在55%左右。此外,一定Na_2CO_3存在下冷却结晶碳酸氢钠晶体形态由细长的针状变为规整的片状。     

东营凹陷民丰地区天然气生成机理与化学动力学研究

民丰地区天然气存在源岩热解和原油裂解成因的争议。本文采用高压釜封闭体系对该区烃源岩和原油样品分别进行了热模拟实验,从烃类气体生成过程、气态烃与部分单体烃生成动力学特征讨论了二者的生气机理,认为原油裂解比源岩热解生气活化能高30～40 kJ/mol,原油比源岩生气需要更高的热力学条件。模拟实验证实,成熟阶段源岩热解气与原油裂解气相比,以环烷烃和芳烃相对含量低为特征,与民丰地区产出的天然气组成更接近,据此认为该区天然气主要为源岩热解成因。     

Secondary copper enrichment in tailings at the Laver mine, northern Sweden

 Field and laboratory studies of the sulphide-bearing tailings at Laver, northern Sweden, show that the present release of metals from the tailings is low, especially with regard to Cu. A large part of the Cu released by sulphide oxidation is enriched in a distinct zone just below the oxidation front. The enrichment zone occurs almost all over the tailings area except in areas with a shallow groundwater table. The Cu enrichment is caused by formation of covellite and adsorption onto mineral surfaces. The transport of Zn, Co, Cd, Ni and S seems to be controlled mainly by adsorption. No secondary zone or secondary minerals containing these metals have been found. Just below the groundwater table, metals are released into solution when the enrichment zone reaches the groundwater due to the low pH. An increased release of metals, especially Cu, can be expected in the future, since the enrichment zone is moving towards the groundwater table. Received: 4 December 1997 · Accepted: 17 December 1998     

The clustered nucleation and growth processes of garnet in regional metamorphic rocks from north-west Connecticut,USA

Serial sectioning and imaging with a flatbed scanner yielded the three-dimensional size and spatial distribution of garnet porphyroblasts in two garnet schists and one staurolite-bearing schist from the Everett Formation, north-west Connecticut. The dominant garnet-producing reaction in all samples was chlorite+quartz=garnet+H₂O. The appearance of staurolite, and additional garnet growth in the staurolite-bearing sample, was due to the reaction chloritoid=garnet+staurolite+chlorite. Statistical measures of garnet spatial distributions, using the pair correlation function (PCF), indicate that garnet crystals are weakly to strongly clustered at length scales between 2 and 10 mm. Such clustered nucleation may reflect minor bulk compositional variations. Covariance measures between garnet size and nearest-neighbour distance, using the mark covariance function (MCF), suggest a very weak correlation between crystal size and nearest-neighbour distance for length scales of 2 mm or less. These statistical data suggest that if diffusional gradients were present around growing garnet crystals, they did not influence nucleation and growth patterns at length scales greater than c. 2 mm. Compositional maps, through the garnet centres, show that the smaller crystals have lower Mn core compositions relative to larger crystals, consistent with progressive nucleation during pro-grade metamorphism. Radius-rate plots calculated from compositional X-ray maps show similar growth rates for garnet crystals of different size, consistent with an interface-controlled growth model for garnet. The presence of minor diffusional gradients around growing garnet cannot be entirely dismissed, but the lack of observable reaction rims, the clustered spatial distribution and the radius-rate data are most consistent with an interface-controlled garnet growth model.