碳酸盐岩风化和成土过程的重金属迁移富集机理初探及环境风险评价

为了探究碳酸盐岩在风化和成土过程中重金属元素迁移规律及重金属的富集机理,本次研究以贵州省都匀市及其周边地区寒武纪地层出露的碳酸盐岩风化剖面为研究对象,采用碳酸盐岩酸不溶物的提取试验研究重金属在基岩中的赋存特征,并结合质量平衡法探索重金属的迁移特征,初步讨论了土壤中重金属的富集机制及其环境影响。研究结果表明：碳酸盐岩风化过程中Ca、Mg元素大量淋失所导致的体积和质量的巨大损失,是造成风化土壤重金属相对富集的主要原因;而部分碳酸盐岩风化过程中释放的重金属以多种形式滞留于残积土中,导致土壤中重金属富集程度增加。研究区部分碳酸盐岩风化剖面重金属含量严重超标,其中以Cd和As超标程度最为严重。重金属元素在碳酸盐岩风化剖面中的迁移规律受气候、剖面发育程度、元素地球化学性质和重金属在碳酸盐岩不同矿物相中的分配特征等多重因素控制。综合分析认为碳酸盐岩风化和成土过程中重金属显著富集的特征很可能是喀斯特地区土壤重金属超标的重要驱动机制,建议地方政府及相关部门在规划和发展农业产业时,要高度重视Cd和As超标的风险,加大对喀斯特地区地表径流和地下水重金属污染的监控力度。     

氟化钙污泥处置及资源化利用

综述了现有的氟化钙污泥处理处置技术,包括浮选富集回用氟化钙,熔融焚烧实现减量化,应用于陶瓷、水泥、混凝土制作,以及利用其化学性质,作为添加剂用于飞灰的固化稳定,或者在钢铁行业中充当萤石成为助熔剂。理论分析和试验检测表明上述方法均可实现含氟污泥的减量化、无害化、资源化,在处理氟化钙污泥时可以根据实际情况选择相应的工艺技术。     

A novel method to make regenerable core-shell calcium-based sorbents

A sorbent having a calcium oxide core and a clay shell was prepared and shown to be capable of reusable applications in absorption and desorption processes for carbon dioxide. The novelty of this sorbent is that only calcium carbonate and clay are used for its preparation with water as a binder. A two-step granulation procedure is used to get the core and then another step to coat the shell layer with the clay powder. A repeated wet-and-dry procedure probably makes the core porous yet strong enough to serve as a sorbent. The pellet is then calcined at 1200 degrees C for 2h to reach its final structure. The core-shell pellets have an overall diameter of 4.4mm with average shell thickness of 0.45 mm, crush load of 35 N and attrition index of 0.035 wt%/h. These results indicate that the pellets will probably be capable of withstanding the stress in future applications. Carbon dioxide absorption at or below 300 degrees C showed a maximum weight gain of 38% for our pellets. Finally, desorption in nitrogen at 800 degrees C can restore the pellet to its original state and hence it is ready for re-use as a sorbent.     

Post-combustion CO2-capture from coal-fired power plants: Preliminary evaluation of an integrated chemical absorption process with piperazine-promoted potassium carbonate

The simulation tool ASPEN Plus^® is used to model the full CO₂-capture process for chemical absorption of CO₂ by piperazine-promoted potassium carbonate (K₂CO₃/PZ) and the subsequent CO₂-compression train. Sensitivity analysis of lean loading, desorber pressure and CO₂-capture rate are performed for various solvent compositions to evaluate the optimal process parameters. EbsilonProfessional^® is used to model a 600 MW_el (gross) hard coal-fired power plant. Numerical equations for power losses due to steam extraction for solvent regeneration are derived from simulation runs. The results of the simulation campaigns are used to find the process parameters that show the lowest specific power loss. Subsequently, absorber and desorber columns are dimensioned to evaluate investment costs for these main components of the CO₂-capture process. Regeneration heat duty, net efficiency losses and column investment costs are then compared to the reference case of CO₂-capture by monoethanolamine (MEA).CO₂-capture by piperazine-promoted potassium carbonate with subsequent CO₂-compression to 110 bar shows energetic advantages over the reference process which uses MEA. Additionally, investment costs for the main components in the CO₂-capture process (absorber and desorber columns) are lower due to the enhanced reaction kinetics of the investigated K₂CO₃/PZ solvent which leads to smaller component sizes.     

Synthesis of calcium phosphate hydrogel from waste incineration fly ash and its application to fuel cell

Waste incineration fly ash was successfully recycled to calcium phosphate hydrogel, a type of fast proton conductor. The crystallized hydrogel from incineration fly ash had a lower electric conductivity and a lower crystallinity than that from calcium carbonate reagent. However, the difference in electric conductivity between these crystallized hydrogels decreases with temperature. This was due to the presence of potassium in the incineration fly ash. The fuel cell with a membrane electrode assembly (MEA) using the calcium phosphate hydrogel membrane prepared from incineration fly ash was observed to generate electricity. The performance of this fuel cell was almost equal to that of a mixture of K₂CO₃ and CaCO₃ reagents; further, the performance of the former was superior to the fuel cell with a perfluorosulfonic polymer membrane at temperatures greater than approximately 85 °C.     

Viable chemical recycling of poly(carbonate) as a phosgene equivalent illustrated by the coproduction of bisphenol A and carbohydrate carbonates

Chemical recycling of waste poly(carbonate) (PC) to coproduce bisphenol A (BPA) and carbohydrate carbonates was studied by selecting glycerol (Gly) and glucose (Glu) as model carbohydrates (CHs). In advance of the reaction of PC with CHs, reactions with diphenyl carbonate were examined as a model PC. In dioxane at 100°C using NaOH as catalyst, Gly was converted to cyclic carbonate hydroxymethyldioxolane (HMDO) at 98% and Glu was converted to the dicarbonate (Glu-DC) at 46%, in pyridine, in addition to the production of phenol. Similar treatment of PC with Gly using KOH as a catalyst produced HMDO and BPA at very high yields and treatment with Glu produced Glu-DC and BPA in 38%–42% yields. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6     

Characterization of the pattern of the nongenomic signaling pathway through which TCDD-induces early inflammatory responses in U937 human macrophages

2,3,7,8-Tetrachlorodibenzo(p)dioxin (TCDD) has been known to induce inflammatory signaling in a number of cell types and tissues. We found that in U937 macrophages TCDD causes rapid activation of cytosolic phospholipase A2 (cPLA2) within 30 min as judged by the increase in the serine 505 phosphorylated form of cPLA2 protein and the increased cellular release of free arachidonic acid. This initial action of TCDD is accompanied with the up-regulation of an important inflammation marker, COX-2 mRNA expression within 1 h, and by 3 h, several other markers become up-regulated. These effects appear to be dependent on the initial increase in the intracellular concentration of Ca²⁺, and activation of cPLA2 and COX-2. A comparative study among three different human cell lines showed that activation of COX-2 within 1 h of action of TCDD is a common feature exhibited by all cell lines. On the other hand, the U937 macrophage line appears to be unique among them with respect to its ability to activate TNF-α and IL-8 mRNA expressions, and not requiring Src kinase in propagating the initial signaling of cPLA2. Based on the rapidity of activation of cPLA2 and COX-2, which occurs within 1 h of cell exposure to TCDD, when no change in mRNA expression of CYP1A1 has been observed, it is apparent that this unique action of TCDD is carried out through a distinct “nongenomic” pathway which, is clearly discernable from the classical, “genomic” action pathway of the AhR by not requiring the participation of ARNT.     

Breeding performance of blue tits (Cyanistes caeruleus) and great tits (Parus major) in a heavy metal polluted area

We compared heavy metal levels, calcium levels, breeding parameters and condition of nestling and adult Cyanistes caeruleus and Parus major along a heavy metal pollution gradient. Both species started laying earlier and showed inferior nestling growth and smaller fledging probability in the polluted areas, which are phenologically advanced in spring due to sparse forests. The major inter-specific difference in the responses was that the clutch size and hatching success were decreased in the polluted area in P. major, but not in C. caeruleus. Heavy metal profiles in nestling feces were relatively similar in the two species, though Ni and Pb levels were higher in C. caeruleus than in P. major. However, the latter species showed markedly higher fecal calcium concentrations. Lower calcium levels and higher levels of some heavy metals in C. caeruleus suggest that in Ca-deficient environments this species might be more susceptible to negative pollution effects than P. major.     

Transfer of Sr into fish in Finnish lakes

The long-term behavior of ⁹⁰Sr was investigated from 1987 to 1997 in fifteen lakes in southern and central Finland following the 1986 Chernobyl accident. Both water and fish samples (perch, pike, vendace) were analyzed. ⁹⁰Sr stays long in the freshwater ecosystem; the observed half-lives during the study period were generally around 10 years in water and even longer in fish. One lake exhibited very different behavior for ⁹⁰Sr, with elevated levels in fish and water and very short observed half-life in fish, less than 2 years. Concentration factors of ⁹⁰Sr in fish (Bqkg⁻¹ f.w. in fish/Bqkg⁻¹ in water) among the studied lakes significantly correlated with both the Ca concentration and electrical conductivity of the water. More ⁹⁰Sr was transferred into fish in lakes with a low electrical conductivity and a low Ca concentration. Among other water parameters evaluated were pH, color, total nitrogen, and phosphorus.     

Preparation of calcium oxalate—bromopyrogallol red inclusion sorbent and application to treatment of cationic dye and heavy metal wastewaters

Background, aim, and scope  Dye pollutants are a major class of environmental contaminants. Over 100,000 dyes have been synthesized worldwide and more than 700,000 tons are produced annually and over 5% are discharged into aquatic environments. The adsorption or sorption is one of the most efficient methods to remove dye and heavy metal pollutants from wastewater. However, most of the present sorbents often bear some disadvantages, e.g. low sorption capacity, difficult separation of spoil, complex reproduction, or secondary pollution. Development of novel sorbents that can overcome these limitations is desirable. Materials and methods  On the basis of the chemical coprecipitation of calcium oxalate (CaC₂O₄), bromopyrogallol red (BPR) was embedded during the growing of CaC₂O₄ particles. The ternary C₂O₄ ^2––BPR–Ca²⁺ sorbent was yielded by the centrifugation. Its composition was determined by spectrophotometry and AAS, and its structure and morphology were characterized by powder X-ray diffraction (XRD), laser particle-size analysis, and scanning electron microscopy (SEM). The adsorption of ethyl violet (EV) and heavy metals, e.g. Cu(II), Cd(II), Ni(II), Zn(II), and Pb(II) were carried out and their removal rate determined by spectrophotometry and ICP-OES. The adsorption performance of the sorbent was compared with powder activated carbon. The Langmuir isothermal model was applied to fit the embedment of BPR and adsorption of EV. Results  The saturation number of BPR binding to CaC₂O₄ reached 0.0105 mol/mol and the adsorption constant of the complex was 4.70 × 10⁵ M^–1. Over 80% of the sorbent particles are between 0.7 and 1.02 μm, formed by the aggregation of the global CaC₂O₄/BPR inclusion grains of 30–50 nm size. Such a material was found to adsorb cationic dyes selectively and sensitively. Ethyl violet (EV) was used to investigate the adsorption mechanism of the material. One BPR molecule may just bind with one EV molecule. The CaC₂O₄/BPR inclusion material adsorbed EV over two times more efficiently than the activated carbon. The adsorption of EV on the CaC₂O₄/BPR inclusion sorbent was complete in only 5 min and the sedimentation complete in 1 h. However, those of EV onto activated carbon took more than 1.5 and 5 h, respectively. The treatment of methylene blue and malachite green dye wastewaters indicated that only 0.4% of the sorbent adsorbed over 80% of color substances. Besides, the material can also adsorb heavy metals by complexation with BPR. Over 90% of Pb²⁺, and approximately 50% of Cd²⁺ and Cu²⁺, were removed in a high Zn²⁺-electroplating wastewater when 3% of the material was added. Eighty-six percent of Cu²⁺, and 60% of Ni²⁺ and Cd²⁺, were removed in a high Cd²⁺-electroplating wastewater. Discussion  The embedment of BPR into CaC₂O₄ particles responded to the Langmuir isothermal adsorption. As the affinity ligand of Ca²⁺, BPR with sulfonic groups may be adsorbed into the temporary electric double layer during the growing of CaC₂O₄ particles. Immediately, C₂O₄ ^2– captured the Ca²⁺ to form the CaC₂O₄ outer enclosed sphere. Thus, BPR may be released and embedded as a sandwich between CaC₂O₄ layers. The adsorption of EV on the sorbent obeyed the Langmuir isothermal equation and adsorption is mainly due to the ion-pair attraction between EV and BPR. Different from the inclusion sorbent, the activated carbon depended on the specific surface area to adsorb organic substances. Therefore, the adsorption capacity, equilibrium, and sedimentation time of the sorbent are much better than activated carbon. The interaction of heavy metals with the inclusion sorbent responded to their coordination. Conclusions  By characterizing the C₂O₄ ^2––BPR–Ca²⁺ inclusion material using various modern instruments, the ternary in situ embedment particle, [(CaC₂O₄)₉₅(BPR)] _n ^2n–, an electronegative, micron-sized adsorbent was synthesized. It is selective, rapid, and highly effective for adsorbing cationic dyes and heavy metals. Moreover, the adsorption is hardly subject to the impact of electrolytes. Recommendations and perspectives  The present work provides a simple and valuable method for preparing the highly effective adsorbent. If a concentrated BPR wastewater was reused as the inclusion reactant, the sorbent will be low cost. By selecting the inclusion ligand with a special structure, we may prepare some particular functional materials to recover the valuable substances from seriously polluted wastewaters. The recommended method will play a significant role in development of advanced adsorption materials. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.