Effect of pH and coexisting anions on removal of phosphate from aqueous solutions by inorganic-based mesostructures

This study investigated the effect of pH and the presence of coexisting (competitive) anions on the removal of phosphate by titanium mesostructures synthesized using do- or hexadecyltrimethylammonium bromide. To address these research objectives, experiments were conducted (1) under controlled initial pH values (2 to 10); and (2) through injection of nitrate, fluoride, chloride, or sulfate anions into a phosphate solution. Based on the experimental results, an initial of pH of 2 was found to be optimal for use of titanium mesostructures. The presence of fluoride anions in solution significantly decreased the removal efficiency of phosphate removal (3.56% at 3.95 mg/g). However, the addition of nitrate, chloride, and sulfate anions did not affect phosphate removal.     

A long-term performance test on an autotrophic denitrification column for application as a permeable reactive barrier

The long-term performance of a sulfur-based reactive barrier system was evaluated using autotrophic denitrification in a large-scale column. A bacterial consortium, containing autotrophic denitrifiers attached on sulfur particles, serving as an electron donor, was able to transform 60mgNL(-1) of nitrate into dinitrogen. In the absence of phosphate, the consortium was unable to remove nitrate, but after the addition of phosphate, nitrate removal was readily evident. Once the column operation had stabilized, seepage velocities of 1.0x10(-3) and 0.5x10(-3)cms(-1), corresponding to hydraulic residence times of 24 and 48h, respectively, did not affect the nitrate removal efficiency, as determined by the nitrate concentration in the effluent. However, data on the nitrate, nitrite and sulfate distribution along the column indicated differential transformation patterns with column depths. Based on the dinitrogen concentration in the total gas collected, the denitrification efficiency of the tested column was estimated to be more than 95%. After 500d operation, the hydrodynamic characteristics of the column slightly changed, but these changes did not inhibit the nitrate removal efficiency. Data from a bacterial community analysis obtained from four parts of the column demonstrated the selective a spatial distribution of predominant species depending on available electron acceptors or donors.     

Mechanisms of phosphorus removal by cement-bound ochre pellets

Hydrous ferric oxide (here termed ‘ochre’) sludge, an abundant waste product produced from the treatment of acid mine drainage (AMD), was used in this study for the removal of phosphorus (in the form of phosphate ions) from contaminated waters. The phosphorus uptake capacities of both raw and pelletized AMD solids were compared using batch and column tests. Addition of a cement binder to the AMD solids during pellet production led to significantly increased P-loading of the resultant solids compared to the raw sludge. Additionally, the pellets were found to continue to remove P in tests up to 7 d in duration whereas the unbound AMD sludge appeared to approach equilibrium with phosphate solution after approximately 60 min of contact time. In line with previous studies P uptake by the AMD solids was found to be primarily via adsorption. By contrast calcium phosphate precipitation was found to be the dominant removal mechanism for the cement-bound ochre pellets with a relatively small proportion of removal attributable to the AMD solids. SEM–EDX analysis of the surface of used pellets showed a Ca:P molar ratio close to that of hydroxyapatite (HAP). Continuous column tests on these pellets showed a rapid decrease in P removal capacity by the pellets over time, attributable to the formation of a passivating HAP surface layer.     

Chemical composition of fresh snowfalls at Palmer Station,Antarctica

A first time investigation was performed to establish a chemical baseline for snowfall at Palmer Station Antarctica (64°46′S, 64°05′W) since there was no such record. A chemical baseline for snow could be use to validate climate change studies based on ice core analyses. The snow samples contained (from high to low mass concentration) total organic carbon, chloride, inorganic carbon, sodium, sulfate, magnesium, calcium, potassium, fluoride, ammonium, and nitrate, excluding hydrogen and hydroxide. The pH of these samples ranged between 4.0–6.2. The relatively low nitrate and relatively high sulfate concentrations found in our samples are consistent with the results of other studies for this region of Antarctica. The ions and pH do not appear to favor a particular wind direction during this period. The total deposition of sulfate and flouride via snowfall between 10 January and 10 February is conservatively estimated to be 4.78 and 1.3 kg km^-2, respectively.     

Removal of phosphate from water by a highly selective La(III)-chelex resin

A new polymer ligand exchanger (PLE) has been developed for the removal of phosphate in wastewater. This PLE, consisting of lanthanum(III) bound to chelex-100 resin, was prepared by passing LaCl3 solution through a column of chelex-100. Uptake of phosphate from water by this La-chelex resin was investigated in the column mode. The La-chelex resin was able to remove phosphate efficiently from water, and the uptake of phosphate was not affected by the presence of large amounts of anions (0.1M) such as chloride and sulfate. The La-chelex resin was also able to efficiently remove phosphate from seawater to <0.1mg-Pl(-1), and regenerated for reuse by removing the sorbed phosphate by eluting with 6M HCl.     

Fluoride removal performance of a novel Fe-Al-Ce trimetal oxide adsorbent

A trimetal oxide was developed as a fluoride adsorbent by coprecipitation of Fe(II), Al(III) and Ce(IV) salt solutions with a molar ratio of 1:4:1 under alkaline condition. The material retained amorphous structure and maintained relatively stable fluoride adsorption performance at calcination temperatures lower than 600 degrees C. The optimum pH range for fluoride adsorption was 6.0-6.5 and the adsorbent also showed high defluoridation ability around pH 5.5-7.0, which is preferable for actual application. A high fluoride adsorption capacity of 178 mg g(-1) was acquired under an equilibrium fluoride concentration of 84.5 mg l(-1), adsorbent dose of 150 mg l(-1) and pH 7.0. The adsorption isotherm could be better described by the two-site Langmuir model than the one-site model, suggesting the existence of two types of active sites on the adsorbent surface. Coexistence of high concentrations of phosphate or arsenate only led to partial inhibition of fluoride adsorption, which further suggests the existence of heterogeneous adsorption sites. Sulfate and chloride did not affect fluoride adsorption, and nitrate influenced it only when the concentration of NO(3)(-)-N exceeded 50 mg l(-1). A high desorption efficiency of 97% was achieved by treating fluoride loaded Fe-Al-Ce oxide with NaOH solution at pH 12.2. A column experiment using the adsorbent fabricated into 1mm pellets was performed at an initial fluoride concentration of 5.5 mg l(-1), space velocity of 5h(-1) and pH of 5.8, and 2240 bed volumes were treated with the effluent fluoride under 1.0 mg l(-1).     

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。     

硝酸盐浓度及投加方式对反硝化除磷的影响

采用SBR反应器，详细研究了硝酸盐浓度及其投加方式对反硝化除磷过程的影响。结果表明，缺氧环境下的反硝化吸磷速率与作为电子受体的硝酸盐浓度有很大的关系，硝酸盐浓度越高．吸磷速率越快。当硝酸盐浓度较低．不足以氧化反硝化聚磷菌细胞内的PHB从而导致体系反硝化除磷效率的下降。相同浓度的硝酸盐，采用流加的方式可以获得比一次性投加更高的反硝化吸磷速率。缺氧环境下，反硝化脱氮量与磷的吸收量成良好的线性关系．借助于反硝化聚磷菌，反硝化脱氮与除磷可在一种环境中完成，有效解决了废水中COD不足的问题．同时达到了节省能源和降低污泥产量的目的。     

Ammonia removal from pretreated methane fermentation effluent through a soil trench system: a column experiment

In order to find the optimal running conditions and mechanisms of ammonia removal through a soil trench system that is designed for treating pretreated methane fermentation effluent, a soil column whose structure was similar to the soil trench system was prepared, and irrigated with wastewater below 30 °C. At the beginning, ammonia was mainly adsorbed by the soils, and the ammonia adsorption capacity of soils gradually saturated. After the 12th day, nitrification began in the soil column; the ammonia in the soil column decreased sharply, and the nitrite and nitrate peak appeared sequentially as the wastewater application rate decreased from 0.74 to 0.37 l h⁻¹. When the nitrification in the soil column reached a steady-state, 98% of all the ammonia in the influent was transformed into nitrate.

By changing the running conditions such as temperature, aeration, and wastewater application rate, it was found that the ammonia removal efficiency can be improved by aeration and impeded by low temperature. In these three variables, wastewater application rate has much greater affect on the ammonia removal efficiency; a lower wastewater application rate can increase the ammonia removal efficiency substantially because of the longer travel time.     

Microbial reduction of nitrate in the presence of nanoscale zero-valent iron

Microbial reduction of nitrate in the presence of nanoscale zero-valent iron (NZVI) was evaluated to assess the feasibility of employing NZVI in the biological nitrate treatment. Nitrate was completely reduced within 3 d in a nanoscale Fe(0)-cell reactor, while only 50% of the nitrate was abiotically reduced over 7 d at 25 °C. The removal rate of nitrate in the integrated NZVI-cell system was unaffected by the presence of high amounts of sulfate. Efficient removal of nitrate by Fe(II)-supported anaerobic culture in 14 d indicated that Fe(II), which is produced during anaerobic iron corrosion in the Fe(0)-cell system, might act as an electron donor for nitrate. Unlike abiotic reduction, microbial reduction of nitrate was not significantly affected by low temperature conditions. This study demonstrated the potential applicability of employing NZVI iron as a source of electrons for biological nitrate reduction. Use of NZVI for microbial nitrate reduction can obviate the disadvantages associated with traditional biological denitrification, that relies on the use of organic substrates or explosive hydrogen gas, and maintain the advantages offered by nano-particle technology such as higher surface reactivity and functionality in suspensions.     

Removal of arsenic from groundwater by micellar-enhanced ultrafiltration (MEUF)

The removal characteristics of arsenate using micellar-enhanced ultrafiltration (MEUF) were investigated. Among four different cationic surfactants used, hexadecylpyridinium chloride (CPC) showed the highest removal efficiency of arsenic (96%), and the removal efficiency with hexadecyltrimethylammonium bromide (CTAB) was 94%. But the removal efficiency with benzalkonium chloride (BC) was the lowest (57%) due to higher critical micelle concentration (CMC) of BC than those of other surfactants. Over 80% of arsenic was removed with octadecylamine acetate (ODA). On the effect of solution pH on the arsenic removal, since the valance of arsenate decreases from trivalent to monovalent as pH decreases, the removal was reduced at lower pH. The presence of 0.45mM of nitrate and 0.01mM of phosphate reduced the removal efficiency by 5-8%. This decrease was because of the competition between the arsenate, nitrate and phosphate for the binding sites of the surfactant micelle. Similar decrease in the removal of arsenate was observed with CPC, CTAB and ODA in the presence of these anions. In cross-flow filtration, the removal efficiency of arsenic was similar to that in the dead-end system. However, the decline in flux was less than that in dead-end filtration. In order to lower the concentration of the surfactant in the effluent, the effluent was treated with powdered activated carbon (PAC) before discharging to the environment. Over 98% surfactant was removed with 1gl(-1) of PAC. In conclusions, the MEUF is considered as a feasible process using CPC or CTAB to remove the arsenate from groundwater compared with the other solid based adsorbent processes.     

Effects of fluoride on soil fauna mediated litter decomposition

To evaluate the effect of potentially toxic compounds on soil fauna mediated carbon and other mineral fluxes in poplar litter, a terrestrial micro-ecosystem (MES) was developed, with the isopod Porcellio scaber as a representative soil fauna species. An experiment was conducted, in which MES with isopods were compared to MES without isopods. Potassium fluoride was used as a model compound. The isopods influenced the microbial respiration negatively. No effect was found for the isopods on the nitrogen and phosphorus mineralization. After the first four weeks of the experiment the total respiration of the MES was increased and the phosphate concentration decreased at the highest fluoride concentration. After nine weeks, fluoride decreased ammonium, nitrate and phosphate concentrations in the litter. It is concluded that nitrogen and phosphorus mineralization in the MES are more sensitive to effects of fluoride that microbial respiration. The no observed effect concentrations for net mineralization of ammonium, nitrate and phosphorus were, respectively, 17, 5.3 and 53 micromol fluoride per gram dry weight of litter. Fluoride seems to be toxic for microbial processes at concentrations found in moderately polluted areas.     

Hydration properties of eco-cement pastes from waste sludge ash clinkers

Three types of hydraulic cements have been developed by incorporating sludge ash from a primary sewage treatment plant and a water purification plant, as well as slag from steelworks (ferrate), as a partial replacement for clay, silica, alumina, and iron oxide in raw cement meal. The raw meal for the pre-determined recipes was prepared by heating it to 1400 degrees C for 6 hr in a clinkerization process, using a simulated incinerator and smelter. The major components of ordinary Portland cement, C3S, C2S, C3A, and C4AF, were all found in the clinkers. Of the three types of eco-cements, the eco-cement A paste was most similar to ordinary Portland cement in terms of composition and compressive strength development, while the eco-cement B paste showed early strength development. The differential thermal analysis species analyses indicated that the hydrates in the eco-cement pastes were mainly calcium hydroxide and CSH gels, like those found in ordinary Portland cement paste. Moreover, the degree of hydration, as determined by nuclear magnetic resonance, increased in all eco-cement pastes with an increasing curing age. The results indicate that it indeed is feasible to use sludge ash and ferrate to replace up to 20% of the mineral components of raw materials for cement.     

Major-ion chemistry of the Rocky Mountain snowpack,USA

During 1993–97, samples of the full depth of the Rocky Mountain snowpack were collected at 52 sites from northern New Mexico to Montana and analyzed for major-ion concentrations. Concentrations of acidity, sulfate, nitrate, and calcium increased from north to south along the mountain range. In the northern part of the study area, acidity was most correlated (negatively) with calcium. Acidity was strongly correlated (positively) with nitrate and sulfate in the southern part and for the entire network. Acidity in the south exceeded the maximum acidity measured in snowpack of the Sierra Nevada and Cascade Mountains. Principal component analysis indicates three solute associations we characterize as: (1) acid (acidity, sulfate, and nitrate), (2) soil (calcium, magnesium, and potassium), and (3) salt (sodium, chloride, and ammonium). Concentrations of acid solutes in the snowpack are similar to concentrations in nearby wetfall collectors, whereas, concentrations of soil solutes are much higher in the snowpack than in wetfall. Thus, dryfall of acid solutes during the snow season is negligible, as is gypsum from soils. Snowpack sampling offers a cost-effective complement to sampling of wetfall in areas where wetfall is difficult to sample and where the snowpack accumulates throughout the winter.     

Effect of biochar amendment on sorption and leaching of nitrate, ammonium, and phosphate in a sandy soil

When applied to soils, it is unclear whether and how biochar can affect soil nutrients. This has implications both to the availability of nutrients to plants or microbes, as well as to the question of whether biochar soil amendment may enhance or reduce the leaching of nutrients. In this work, a range of laboratory experiments were conducted to determine the effect of biochar amendment on sorption and leaching of nitrate, ammonium, and phosphate in a sandy soil. A total of thirteen biochars were tested in laboratory sorption experiments and most of them showed little/no ability to sorb nitrate or phosphate. However, nine biochars could remove ammonium from aqueous solution. Biochars made from Brazilian pepperwood and peanut hull at 600 °C (PH600 and BP600, respectively) were used in a column leaching experiment to assess their ability to hold nutrients in a sandy soil. The BP600 biochar effectively reduced the total amount of nitrate, ammonium, and phosphate in the leachates by 34.0%, 34.7%, and 20.6%, respectively, relative to the soil alone. The PH600 biochar also reduced the leaching of nitrate and ammonium by 34% and 14%, respectively, but caused additional phosphate release from the soil columns. These results indicate that the effect of biochar on the leaching of agricultural nutrients in soils is not uniform and varies by biochar and nutrient type. Therefore, the nutrient sorption characteristics of a biochar should be studied prior to its use in a particular soil amendment project.     

Immobilization of lead in shooting range soils by means of cement, quicklime, and phosphate amendments

BACKGROUND, AIM, AND SCOPE: Lead (Pb) contamination at shooting range sites is increasingly under environmental concern. Controlling Pb leachability from shooting range soil media is an important step to minimize Pb exposure to the surrounding environment. This study investigated stabilization of Pb in shooting range soils treated with cement, quicklime, and phosphate. MATERIALS AND METHODS: Two soils were used and collected from two shooting ranges, referred to as SR1 and SR2. The treatment additives were applied to the soils at rates from 2.5% to 10% (w/w). The effectiveness of each treatment was evaluated by Pb (w/w). The effectiveness of each treatment was evaluated by Pb leachability, measured by the Toxicity Characteristic Leaching Procedure (TCLP). The possible mechanisms for Pb immobilization were elucidated using X-ray powder diffraction (XRPD). RESULTS: Cement and quicklime treatments were effective in immobilizing Pb in SR1 soil, with reduction of Pb concentration in TCLP leachate (TCLP-Pb) to be below the U.S. EPA non-hazardous regulatory limit of 5 mg L(-1) at application rates of > or =5% and 28-d incubation. By contrast, cement and quicklime amendments were less effective for Pb stabilization in SR2 soil because the TCLP-Pb levels in the treated soil were still higher than the limit of 5 mg L(-1) at all application rates, although they were significantly reduced in comparison with the untreated soil. Phosphate application was most effective in reducing Pb leach ing in both soils. Even at an application rate as low as 5% and 1-d incubation, phosphate could reduce TCLP-Pb to be below the limit of 5 mg L(-1) in both soils. DISCUSSION: Immobilization of Pb in the SR1 soil amended with cement and quicklime was attributed to the formation of pozzolanic minerals (e.g., calcium silicate hydrate C-S-H and ettringite) that could encapsulate soil Pb. The pozzolanic reaction was limited in the SR2 soil upon the application of cement and quicklime. Reduction of the TCLP-Pb might result from complexation of Pb on the surface of the formed calcite. Phosphate-induced Pb immobilization was mainly attributed to formation of less soluble PbHPO4. CONCLUSIONS: The results indicate that effectiveness of cementitious treatments (cement and quicklime) in immobilizing Pb varies in two soils, being effective in SR1 soil but less in SR2 soil. For one given soil, no difference was observed of the effeciveness between cement and quicklime treatments, whereas phosphate amendment emerges as a most effective treatment means for stabilizing Pb in both two soils, and it also shows a faster immobilization process and little effect on the soil acid buffering capacity. Recommendations and Perspectives. Overall, our study reveals that immobilizing Pb can be one of the best management practices for Pb contamination at shooting range sites. Phosphate amendment is most effective in immobilizing Pb in any kind of the soil ranges to minimize negative Pb impacts on the shooting range sites.     

Effect of biochar amendment on sorption and leaching of nitrate,ammonium, and phosphate in a sandy soil

When applied to soils, it is unclear whether and how biochar can affect soil nutrients. This has implications both to the availability of nutrients to plants or microbes, as well as to the question of whether biochar soil amendment may enhance or reduce the leaching of nutrients. In this work, a range of laboratory experiments were conducted to determine the effect of biochar amendment on sorption and leaching of nitrate, ammonium, and phosphate in a sandy soil. A total of thirteen biochars were tested in laboratory sorption experiments and most of them showed little/no ability to sorb nitrate or phosphate. However, nine biochars could remove ammonium from aqueous solution. Biochars made from Brazilian pepperwood and peanut hull at 600 °C (PH600 and BP600, respectively) were used in a column leaching experiment to assess their ability to hold nutrients in a sandy soil. The BP600 biochar effectively reduced the total amount of nitrate, ammonium, and phosphate in the leachates by 34.0%, 34.7%, and 20.6%, respectively, relative to the soil alone. The PH600 biochar also reduced the leaching of nitrate and ammonium by 34% and 14%, respectively, but caused additional phosphate release from the soil columns. These results indicate that the effect of biochar on the leaching of agricultural nutrients in soils is not uniform and varies by biochar and nutrient type. Therefore, the nutrient sorption characteristics of a biochar should be studied prior to its use in a particular soil amendment project.     

Phosphate removal and recovery with a synthetic hydrotalcite as an adsorbent

Phosphate removal is important to control eutrophication and an ion exchange process is one of several treatment processes for this purpose. Hydrotalcite compounds (HTALs) are useful as adsorbents for phosphate removal because of their ion exchange properties. In this study, the adsorption properties of a granular synthetic HTAL for phosphate and the method of regeneration of the granular HTAL were examined. The adsorption isotherm of the granular HTAL was approximated by a modified Langmuir type, and the maximum adsorption capacity was 47.3 mg P g(-1), which corresponded to the content of HTAL in the granular one. Phosphate adsorbed on the HTAL was effectively desorbed with alkaline NaCl solutions and the HTAL was regenerated with 25 w/v% MgCl(2) solution. The regenerated HTAL could be reused repeatedly for the phosphate removal. Phosphate in the exhausted desorption solution was recovered as a precipitate of calcium phosphate by addition of CaCl(2), and the residual exhausted desorption solution could be also reused after supplying NaOH. The results suggest the possibility of an effective system for phosphate removal and recovery, which includes the following processes: adsorption, desorption, recovery of phosphate, and regeneration of the HTAL and the desorption solution.     

Pozzolanic reactivity of the synthetic slag from municipal solid waste incinerator cyclone ash and scrubber ash

This study investigates the pozzolanic reactions and compressive strength of the blended cement manufactured using synthetic slag obtained from municipal solid waste incinerator (MSWI) cyclone ash and scrubber ash as partial replacement of portland cement. The synthetic slag was made by co-melting the MSWI scrubber ash and cyclone ash mixtures at 1400 degrees C for 30 min. Following pulverization, the different types of slag were blended with cement as cement replacement at ratios ranging from 10 to 40 wt %. The synthetic slag thus obtained was quantified, and the characteristics of the slag-blended cement pastes were examined. These characteristics included the pozzolanic activity, compressive strength, hydration activity, crystal phases, species, and microstructure at various ages. The 90-day compressive strength developed by slag-blended cement pastes with 10 and 20 wt % of the cement replaced by the synthetic slag outperformed ordinary portland cement by 1-7 MPa. X-ray diffraction species analyses indicated that the hydrates in the slag-blended cement pastes were mainly portlandite, the calcium silicate hydrate gels, and calcium aluminate hydrate salts, similar to those found in ordinary portland cement paste. Differential thermal and thermogravimetric analysis also indicated that the slag reacted with portlandite to form calcium silicate hydrate gels.     

固体废弃物对新拌水泥浆体密实度与强度的影响

研究固体废弃物(石灰石粉、粉煤灰、赤泥和矿渣)作掺合料颗粒体系与新拌浆体填充密实性能的关系;分析了在水胶比为0.3时,以上4种固体废弃物以不同比例等质量取代水泥的净浆强度。实验结果表明,石灰石粉、粉煤灰、赤泥作为掺合料,能够改善胶凝材料的颗粒级配,填充新拌水泥浆体中的孔隙,使浆体更为密实,并且对其净浆的强度有利。