A new method to inertize incinerator toxic fly ash with silica from rice husk ash

Fly ash from municipal solid waste incineration is a toxic waste due to the presence of toxic heavy metals. Here, a new method for metal stabilization based on the use of silica gel extracted from rice husk ash is presented. This method is sustainable because of the use of only waste materials to produce a final inert product, and because the inertization procedure occurs at room temperature. The estimated maximum Pb adsorption capacity of extracted silica, of about 36 mg/g, is found to be far greater than the adsorption capacity of other known absorbers used for municipal solid waste incineration fly ash.     

Leaching of arsenic from coal fly ashes 2. Arsenic pre‐leaching with sodium gluconate solution

The present study deals with the development of an efficient and reliable process for safe disposal of coal fly ash to remove arsenic that has been found to be the most easily leachable and hazardous heavy metal in coal fly ash. Pre‐leaching of fly ash prior to disposal by a natural chelating agent, sodium gluconate (SG), was proposed and studied. Several operational factors influencing arsenic leachability, such as concentration of SG solution, liquid to solid ratio, pH, length of leaching time and leaching temperature were examined. Arsenic was found to leach out substantially with SG, but almost no further release was observed from the ash pre‐leached by SG. After the pre‐leaching treatment, the desirable high buffering capacity of the ash was well sustained. SG solution was effectively regenerated by activated alumina adsorption so that it could be successfully reused for multiple leaching/adsorption cycles.     

Effect of natural organic matter on arsenic release from soils and sediments into groundwater

Arsenic (As) contamination in groundwater has received significant attention recently. Natural and anthropogenic sources contribute to the worldwide occurrence of As contamination. As speciation is an important factor related to its toxic and mobile behavior. The release of As from soils and sediments into groundwater is governed by several geophysicochemical processes, of which, As sorption behavior is of principle significance. This review paper summarizes existing information regarding the effects of natural organic matter (NOM) on the fate and mobility of As species in the environment. NOM may enhance the release of As from soils and sediments into the soil solution, thereby facilitating As leaching into the groundwater. The main influencing mechanisms include competition for available adsorption sites, formation of aqueous complexes, and/or changes in the redox potential of site surfaces and As redox speciation. NOM may also serve as binding agents, thereby reducing As mobility. However, comparably little research has been performed on this aspect. Since most investigations have been done on purified minerals under laboratory conditions, further research involving various geological materials under natural environmental conditions is required. Development of proper geochemical conceptual models may provide means of predicting the role of NOM in arsenic leaching and/or immobilization.     

Characteristics of the stabilized/solidified municipal solid wastes incineration fly ash and the leaching behavior of Cr and Pb

Fly ash is a hazardous byproduct of municipal solid wastes incineration (MSWI). An alkali activated blast furnace slag-based cementitious material was used to stabilize/solidify the fly ash at experimental level. The characteristics of the stabilized/solidified fly ash, including metal leachability, mineralogical characteristics and the distributions of metals in matrices, were tested by toxic characteristic leaching procedure (TCLP), X-ray diffraction (XRD) and scanning electron microscopy-energy dispersive spectrometer (SEM-EDS) respectively. Continuous acid extraction was utilized to extract metal ions and characterize their leaching behavior. The stabilization/solidification procedure for MSWI fly ash demonstrates a strong fixing capacity for the metals by the formation of C-S-H phase, hydrated calcium aluminosilicate and ettringite. The stabilized/solidified fly ash shows a dense and homogeneous microstructure. Cr is mainly solidified in hydrated calcium aluminosilicate, C-S-H and ettringite phase through physical encapsulation, precipitation, adsorption or substitution mechanisms, and Pb is mainly solidified in C-S-H phase and absorbed in the Si-O structure.     

Toxic elements leaching in different soils affected by the spill from the aznalcollar pyrite mine (Sevilla,Spain)

A study has been made of the leaching of Cd, Zn, Pb, Cu, Tl and As in three representative soils of the zone affected by the spill from a pyrite mine in Aznalcollar (Sevilla, Spain) employing packed soil columns. According to the breakthrough and cumulative leaching curves, the relative mobilities of the different toxic elements in the columns are as follows: Tl > Cd > Zn > As > Cu > Pb. The results also show that the soils themselves have a good capacity for immobilizing the soluble fraction of the elements from the spilled mud, this capacity varying as follows: clayey soil with a high carbonate content > clayey soil with a moderate carbonate content > sandy‐clay loam soil with a low carbonate content. The results obtained in the work are a valuable contribution to the necessary assessment of the impact of the toxic spill on underground waters.     

Chemical Behaviour of Calcium in Stabilized Oil Ash Reef Blocks After Five Years in the Ocean

Abstract

Reef blocks made from stabilized oil ash were taken from the sea after five years in the ocean to examine the chemical behaviour of calcium. Experiments included (1) determination of the calcium leaching rate and a comparison with the rate for unexposed blocks to test the validity of a diffusion model for predicting long term (5 years) leaching rates, (2) determination of the effect of biological cover (shell) on the leaching rate, (3) determination of the leaching rate of the core of exposed reef blocks, (4) determination of the calcium content in ‘ring areas’ - regions of discoloration observed in sectioned exposed reef blocks, and (5) determination of the leachable fraction of the total calcium in exposed reef blocks. Results showed the presence of a pronounced calcium discontinuity zone located 3–7 cm from the outside surface of the reef blocks. Cumulated calcium release rates ranged from 2.81–3.14 μmol cm^?2 day^?1 for original unexposed reef blocks and the core of exposed (in the ocean for five years) blocks, respectively, to 0.47–0.50 μmol cm^?2 day^?1 for outside (facing sea water) surfaces of exposed reef blocks. Tank leaching studies also showed that the presence or absence of hard biological cover (shells) had little or no effect on the calcium release rate. the diffusion model normally used in modelling the chemical behaviour of calcium cannot be used to predict the long term (five years) leaching of calcium. the core of the exposed blocks released calcium at a rate similar to new, unexposed reef block material. Overall, it appears that the calcium discontinuity zone is probably responsible for restricting the release of calcium and hence the failure of the diffusion model.     

Chemical Behaviour of Calcium in Stabilized Oil Ash Reef Blocks After Five Years in the Ocean

Reef blocks made from stabilized oil ash were taken from the sea after five years in the ocean to examine the chemical behaviour of calcium. Experiments included (1) determination of the calcium leaching rate and a comparison with the rate for unexposed blocks to test the validity of a diffusion model for predicting long term (5 years) leaching rates, (2) determination of the effect of biological cover (shell) on the leaching rate, (3) determination of the leaching rate of the core of exposed reef blocks, (4) determination of the calcium content in 'ring areas' - regions of discoloration observed in sectioned exposed reef blocks, and (5) determination of the leachable fraction of the total calcium in exposed reef blocks. Results showed the presence of a pronounced calcium discontinuity zone located 3-7 cm from the outside surface of the reef blocks. Cumulated calcium release rates ranged from 2.81-3.14 μmol cm^-2 day^-1 for original unexposed reef blocks and the core of exposed (in the ocean for five years) blocks, respectively, to 0.47-0.50 μmol cm^-2 day^-1 for outside (facing sea water) surfaces of exposed reef blocks. Tank leaching studies also showed that the presence or absence of hard biological cover (shells) had little or no effect on the calcium release rate. the diffusion model normally used in modelling the chemical behaviour of calcium cannot be used to predict the long term (five years) leaching of calcium. the core of the exposed blocks released calcium at a rate similar to new, unexposed reef block material. Overall, it appears that the calcium discontinuity zone is probably responsible for restricting the release of calcium and hence the failure of the diffusion model.     

海洋酸化与重金属、有机污染物和人工纳米颗粒的联合毒性效应研究进展

由于大量人类活动的影响,大气CO_2浓度持续增加,其中约1/3被海洋吸收,导致表层海水pH值降低和碳酸盐平衡体系波动,即"海洋酸化"现象。污染物的海洋环境效应一直是全球环境科学领域研究的热点。在实际环境中,海洋酸化往往与污染物共同存在并作用于海洋生态系统,且海洋酸化极有可能改变污染物的海洋环境行为从而影响其毒性效应。但现有研究大多针对海洋酸化或者污染物单独作用下的毒性效应展开,对海洋酸化与污染物的联合毒性效应的研究不足、亟待加强。为此,综述了近年来海洋酸化与典型污染物(重金属、有机污染物)及新型污染物(人工纳米颗粒)的相关文献,重点阐述了海洋酸化对污染物环境行为的影响和海洋酸化与污染物对海洋生物的联合毒性效应,指出当前的研究不足,并对未来的研究方向进行了展望。     

Mobilization of arsenic from technosols in a short-term dynamic column experiment

The release of arsenic from technosols was monitored using short-term dynamic leaching of homogeneous soil columns with native solution. Large amounts of readily available arsenic (16 mg kg^?1) were extracted from arsenic-rich ashy samples while representing less than 4 wt % of their total contents. In the first hour of leaching, the observed concentrations of water-soluble arsenic ranged from 650 to 830 μg L^?1, further increasing in the following leachates. The results showed that the concentrations of water-soluble arsenic were several times higher than the recommended limits for drinking water. Yet, most of arsenic is strongly bound to amorphous aluminosilicate phases. The contents of arsenic in the studied plant samples, including calculated transfer factors, confirmed that increased concentrations of arsenic in the soil of geological environment affected by dam failure of a coal ash pond may have a negative effect on crops since arsenic becomes part of the food chain.     

Phosphates for Pb immobilization in soils: a review

In its soluble ionic forms, lead (Pb) is a toxic element occurring in waters and soils mainly as the result of human activities. The bioavailability of lead ions can be decreased by complexation with various materials in order to decrease their toxicity. Pb chemical immobilization using phosphate addition is a widely accepted technique to immobilize Pb from aqueous solution and contaminated soils. The application of different P amendments cause Pb in soils to shift from forms with high availability to the most strongly bound Pb fractions. The increase of Pb in the residual or insoluble fraction results from formation of pyromorphite Pb₅(PO₄)₃X where X = F, Cl, Br, OH, the most stable environmental Pb compounds under a wide range of pH and Eh natural conditions. Accidental pyromorphite ingestion does not yield bioavailable lead, because pyromorphite is insoluble in the intestinal tract. Numerous natural and synthetic phosphates materials have been used to immobilize Pb: apatite and hydroxyapatite, biological apatite, rock phosphate, soluble phosphate fertilizers such as monoammonium phosphate, diammonium phosphate, phosphoric acid, biosolids rich in P, phosphatic clay and mixtures. The identification of pyromorphite in phosphate amended soils has been carried out by different non destructive techniques such as X-ray diffraction, scanning electron microscopy coupled with energy dispersive X-ray spectroscopy, X-ray absorption fine structure, transmission electron microscopy and electron microprobe analysis. The effectiveness of in situ Pb immobilization has also been evaluated by selective sequential extraction, by the toxicity leaching procedure and by a physiologically based extraction procedure simulating metal ingestion and gastrointestinal bioavailability to humans. Efficient Pb immobilization using P amendments requires increasing the solubility of the phosphate phase and of the Pb species phase by inducing acid conditions. Although phosphorus addition seems to be highly effective, excess P in soil and its potential effect on eutrophication of surface water, and the possibility of As enhanced leaching remains a concern. The use of mixed treatments may be a useful strategy to improve their effectiveness in reducing lead phyto- and bioavailability.     

36种典型除草剂对绿藻的毒性研究

近年来,农药对生态系统的初级生产者——藻类的毒性及其生态毒理学研究引起了国内外学者的广泛关注。除草剂在生产中广泛应用,对藻类的毒性作用最强,其毒性效应远高于杀虫剂和杀菌剂。论文选择市场上具有典型代表性的36种除草剂原药,分析解读除草剂在国内的登记情况,以及在作物、旱田和水田的使用情况;明晰对藻类生长抑制急性毒性效应。结果表明:1)除草剂的作用方式和化学类别对绿藻毒性影响显著;对于抑制植物细胞分裂和作用于植物叶绿体的除草剂对绿藻毒性均较高,以人工合成植物生长素为代表的除草剂对绿藻毒性均较低;2)相同作用方式,不同化学类别的除草剂,对单一绿藻的毒性差异明显。在水稻上获得登记的除草剂对藻类毒性整体低于在旱田获得登记的除草剂对藻类的毒性。开展多种农药对水生生态毒性的研究,为农药的合理安全使用、农药在淡水环境中的生态效应评价以及保护淡水生态系统提供科学依据。     

Effects of sulfur on variations in the chemical speciation of heavy metals from fly ash glass

● A higher sulfur content reduced the curing rate of Cr in glass. ● Depolymerization increased the amounts of heavy metals in the carbonate bound state. ● Reducing the CaO/SiO₂ ratio increased the proportion of stable heavy metals. This work designed a new CaO-Al₂O₃-SiO₂-SO₃ glass for the immobilization of multiple heavy metals found in dechlorinated fly ash having high amounts of calcium and sulfur. Increasing the (CaO + SO₃)/SiO₂ mass ratio (M(CS/S)) from 0.28 to 0.85 was found to lower the proportions of Mn, Ni and Zn in an unstable state, while an M(CS/S) ratio of 0.51 gave the lowest proportions of unstable Cr and Pb. Decreasing the degree of polymerization of the glassy network increased the proportions of Mn, Cr, Ni, Pb and Zn in the carbonate bound state. The leaching out of metals in this state was the primary cause of degradation of Q³ structural units in the glassy network. The amount of Mn in the iron-manganese oxide bound state was increased by increasing the number of Q² units in the silicate network. Decreasing the CaO/SiO₂ mass ratio (M(C/S)) raised the proportions of Mn, Ni and Zn in the unstable state. An M(C/S) value of 0.43 lowered the proportions of unstable Cr and Pb. A principal components analysis determined that the leaching of toxic heavy metals from the glass was primarily related to the proportions of these metals in the unstable state while there were no evident correlations between leaching and the proportions in stable states.     

Unraveling the antibacterial mode of action of a clay from the Colombian Amazon

Natural antibacterial clays can inhibit growth of human pathogens; therefore, understanding the antibacterial mode of action may lead to new applications for health. The antibacterial modes of action have shown differences based on mineralogical constraints. Here we investigate a natural clay from the Colombian Amazon (AMZ) known to the Uitoto natives as a healing clay. The physical and chemical properties of the AMZ clay were compared to standard reference materials: smectite (SWy-1) and kaolinite (API #5) that represent the major minerals in AMZ. We tested model Gram-negative (Escherichia coli ATCC #25922) and Gram-positive (Bacillus subtilis ATCC #6633) bacteria to assess the clay’s antibacterial effectiveness against different bacterial types. The chemical and physical changes in the microbes were examined using bioimaging and mass spectrometry of clay digests and aqueous leachates. Results indicate that a single dose of AMZ clay (250 mg/mL) induced a 4–6 order of magnitude reduction in cell viability, unlike the reference clays that did not impact bacterial survival. AMZ clay possesses a relatively high specific surface area (51.23 m²/g) and much higher total surface area (278.82 m²/g) than the reference clays. In aqueous suspensions (50 mg clay/mL water), soluble metals are released and the minerals buffer fluid pH between 4.1 and 4.5. We propose that the clay facilitates chemical interactions detrimental to bacteria by absorbing nutrients (e.g., Mg, P) and potentially supplying metals (e.g., Al) toxic to bacteria. This study demonstrates that native traditional knowledge can direct scientific studies.     

Gypsum addition to soils contaminated by red mud: implications for aluminium, arsenic, molybdenum and vanadium solubility

Red mud is highly alkaline (pH 13), saline and can contain elevated concentrations of several potentially toxic elements (e.g. Al, As, Mo and V). Release of up to 1 million m³ of bauxite residue (red mud) suspension from the Ajka repository, western Hungary, caused large-scale contamination of downstream rivers and floodplains. There is now concern about the potential leaching of toxic metal(loid)s from the red mud as some have enhanced solubility at high pH. This study investigated the impact of red mud addition to three different Hungarian soils with respect to trace element solubility and soil geochemistry. The effectiveness of gypsum amendment for the rehabilitation of red mud-contaminated soils was also examined. Red mud addition to soils caused a pH increase, proportional to red mud addition, of up to 4 pH units (e.g. pH 7 → 11). Increasing red mud addition also led to significant increases in salinity, dissolved organic carbon and aqueous trace element concentrations. However, the response was highly soil specific and one of the soils tested buffered pH to around pH 8.5 even with the highest red mud loading tested (33 % w/w); experiments using this soil also had much lower aqueous Al, As and V concentrations. Gypsum addition to soil/red mud mixtures, even at relatively low concentrations (1 % w/w), was sufficient to buffer experimental pH to 7.5–8.5. This effect was attributed to the reaction of Ca²⁺ supplied by the gypsum with OH^? and carbonate from the red mud to precipitate calcite. The lowered pH enhanced trace element sorption and largely inhibited the release of Al, As and V. Mo concentrations, however, were largely unaffected by gypsum induced pH buffering due to the greater solubility of Mo (as molybdate) at circumneutral pH. Gypsum addition also leads to significantly higher porewater salinities, and column experiments demonstrated that this increase in total dissolved solids persisted even after 25 pore volume replacements. Gypsum addition could therefore provide a cheaper alternative to recovery (dig and dump) for the treatment of red mud-affected soils. The observed inhibition of trace metal release within red mud-affected soils was relatively insensitive to either the percentage of red mud or gypsum present, making the treatment easy to apply. However, there is risk that over-application of gypsum could lead to detrimental long-term increases in soil salinity.     

Calcium carbonate waste from an integrated pulp and paper mill as a potential liming agent

Calcium carbonate is used in large amounts in the pulp and paper industry as a paper filler. When it is manufactured, the calcium carbonate waste is purged from the process. Here we demonstrate that, due to the elevated calcium concentration of 168.5 g kg⁻¹ dry weight (dw), alkaline pH of 12.6 and neutralizing (liming) effect value of 42.4% expressed as Ca equivalents, this waste is a potential liming agent and a pH buffer. The heavy metal concentrations in the waste were lower than the new Finnish limit values for fertilizers used in agriculture, as well as for a material, e.g. ash, used as an earth construction agent. These limit values came into force in March 2007 and in June 2006, respectively.     

Sorption of pyrene from water by oil shale ash and mineral particles

The aim of this work was to estimate the sorption of pyrene from water solutions on mineral substrates, e.g., alumina, silica, and oil shale ash, from the Estonian thermal plant. Results obtained from this study indicate that the sorption of pyrene on mineral oxides and oil shale ash particles from water can be described with a linear equation. The sorptive capacity per weight of oil shale ash in aqueous systems was significantly lower compared with mineral adsorbents. The distribution coefficient (K_d) for pyrene in the system with particles of oil shale ash was 10–12 times lower as than for mineral adsorbents.     

Leaching Characteristics of Lead and Cadmium From Waste-To-Energy Residues in Sea Water

Laboratory studies were conducted to determine leaching characteristics of waste-to-energy (WTE) residues in sea water to provide initial evaluation on the potential impact of WTE residues on the marine environment. Both loose and stabilized WTE residues were investigated for the leachability of lead (Pb) and cadmium (Cd) in sea water. Results of the study showed that loose WTE fly ash was very reactive in sea water; release of Pb and Cd occurred immediately (<0.5 hr) after the ash came in contact with sea water. Stabilization (treated with Portland cement and other additives), however, significantly reduced leaching of Cd and Pb. While ocean disposal of untreated WTE residues would not be advisable, utilization of stabilized WTE residues for beneficial uses should be investigated.     

Use of zeolitized coal fly ash in the simultaneous removal of ammonium and phosphate from aqueous solution

Discharge of wastewater containing nitrogen and phosphate can cause eutrophication. Therefore, the development of an efficient material for the immobilization of the nutrients is important. In this study, a low calcium fly ash and high calcium fly ash were converted into zeolite using the hydrothermal method. The removal of ammonium and phosphate that coexist in aqueous solution by the synthesized zeolites were studied. The results showed that zeolitized fly ash could efficiently eliminate ammonium and phosphate at the same time. Saturation of zeolite with Ca²⁺ rather than Na⁺ favored the removal of both ammonium and phosphate because the cation exchange reaction by the NH₄ ⁺ resulted in the release of Ca²⁺ into the solution and precipitation of Ca²⁺ with PO₄ ^3? followed. An increase in the temperature elevated the immobilization of phosphate whereas it abated the removal of ammonium. Nearly 60% removal efficiency for ammonium was achieved in the neutral pH range from 5.5 to 10.5, while the increase or decrease in pH out of the neutral range lowered the adsorption. In contrast, the removal of phosphate approached 100% at a pH lower than 5.0 or higher than 9.0, and less phosphate was immobilized at neutral pH. However, there was still a narrow pH range from 9.0 to 10.5 favoring the removal of both ammonium and phosphate. It was concluded that the removal of ammonium was caused by cation exchange; the contribution of NH₃ volatilization to immobilization at alkaline conditions (up to pH level of 11.4) was limited. With respect to phosphate immobilization, the mechanism was mainly the formation of precipitate as Ca₃(PO₄)₂ within the basic pH range or as FePO₄ and AlPO₄ within acidic pH range.     

Laboratory weathering studies of coal refuse

Coal refuse samples from Staunton, Illinois, were continuously leached in soxhlet extractors at 97, 65, 55 and 45°C for up to 192 hr. An identical refuse sample was leached once a week for 11 weeks using a humidity cell at approximately 25°C. Leachate collected from the soxhlet and humidity cell apparatus was analysed for pH, EC, SO₄, Fe, Mn, Al and total acidity.The data indicate that concentrations of SO₄, Fe and Mn increased rapidly as the leaching temperature in the soxhlets increased. Soxhlet extractors removed virtually all soluble Fe and Mn species within 64 hr of leaching. A comparison of the leachate characteristics of the low-temperature soxhlet and humidity cell showed that the soxhlet removed 50% more total Fe and SO₄ for the complete leaching cycle. Pyrite oxidation in the soxhlet extractors was observed near the end of the extraction sequence, but pyrite oxidation in the humidity cell was masked by the release of soluble iron sulphates. Thus, the origin of leachate acidity in the humidity cell could not be distinguished between the soluble mineral phase and the acidity resulting from the oxidation of pyritie minerals.The results of this experiment suggests that the use of the soxhlet extractor for leaching coal refuse may produce a faster and more accurate representation of water quality impacts than would the use of the humidity cell. Long-term leaching studies must be completed to further clarify the role of both these leaching methods for predicting water quality impacts.Contribution of the Land Reclamation Program at Argonne National Laboratory, Argonne, Illinois 60439.     

Healing and edible clays: a review of basic concepts,benefits and risks

The use of clay by humans for medicinal and wellness purposes is most probably as old as mankind. Within minerals, due to its ubiquitous occurrence in nature and easy availability, clay was the first to be used and is still used worldwide. Healing clays have been traditionally used by man for therapeutic, nutritional and skin care purposes, but they could impart some important health and skin care risks. For instance, clay particles could adsorb and make available for elimination or excretion any potential toxic elements or toxins being ingested or produced, but they could adsorb and make available for incorporation, through ingestion or through dermal absorption, toxic elements, e.g. heavy metals. Edible clays, a particular case of healing clays, have been traditionally used by man for nutritional and therapeutic purposes. Geophagy, the deliberate soil eating, earth eating, clay eating and pica (medical condition or eating disorder shown by individuals addicted to eat earth substances), has been observed in all parts of the world since antiquity, reflecting cultural practice, religious belief and physiological needs, be they nutritional (dietary supplementation) or as a remedy for disease. This paper pretends to review historical data, basic concepts and functions, as well as benefits and risks of the use of healing clays, in general, for therapeutic and cosmetic purposes, and of edible clays, in particular, for therapeutic purposes.