Eu uptake by calcite: Preliminary results from coprecipitation experiments and observations with surface-sensitive techniques

A lack of information in databases for contamination risk assessment about the transport behaviour of the trivalent f-orbital elements in groundwater systems where calcite is at equilibrium motivated this study of Eu³⁺ uptake. The free drift technique was used to examine the effects of Eu³⁺ concentration, presence of Na⁺ or K⁺ and temperature, as well as calcite nucleation and precipitation kinetics, on the partitioning of calcite. Changes in surface composition and morphology resulting from exposure of single crystals of Iceland spar to Eu³⁺-bearing solutions were observed with X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). First results confirm that calcite has high affinity for Eu³⁺. Rates of nucleation and precipitation strongly affect the extent of uptake but the presence of Na⁺ and K⁺ has no effect, suggesting formation of solid solution as CaCO₃–EuOHCO₃. Surface-sensitive techniques prove that Eu³⁺ is adsorbed to calcite even when the surface is dissolving and adsorption is not accompanied by precipitation of a separate Eu³⁺-solid phase. Adsorbed Eu modifies calcite's dissolution behaviour, roughening terraces and rounding step edges, and producing surface morphology where some surface sites appear blocked. Results imply that Eu³⁺ concentrations in natural calcites are limited by Eu³⁺ availability rather than by a lack of ability to fit into calcite's atomic structure. This behaviour can probably be expected for other trivalent rare Earth elements (REE), actinides and fission products whose behaviour is similar to that of Eu³⁺. These elements are likely to be incorporated within the calcite bulk in systems where it is precipitating and the demonstrated strong partitioning ensures some uptake even where calcite is at or under saturation.     

Household water insecurity and its cultural dimensions: preliminary results from Newtok,Alaska

Using a relational approach, I examine several cultural dimensions involved in household water access and use in Newtok, Alaska. I describe the patterns that emerge around domestic water access and use, as well as the subjective lived experiences of water insecurity including risk perceptions, and the daily work and hydro-social relationships involved in accessing water from various sources. I found that Newtok residents haul water in limited amounts from a multitude of sources, both treated and untreated, throughout the year. Household water access is tied to hydro-social relationships predicated on sharing and reciprocity, particularly when the primary treated water access point is unavailable. Older boys and young men are primarily responsible for hauling water, and this role appears to be important to male Yupik identity. Many interviewees described preferring to drink untreated water, a practice that appears related to cultural constructions of natural water sources as pure and self-purifying, as well as concerns about the safety of treated water. Concerns related to the health consequences of low water access appear to differ by gender and age, with women and elders expressing greater concern than men. These preliminary results point to the importance of understanding the cultural dimensions involved in household water access and use. I argue that institutional responses to water insecurity need to incorporate such cultural dimensions into solutions aimed at increasing household access to and use of water.     

木屑和花生壳吸附去除水溶液中Cr3+的试验研究

以废弃物木屑和花生壳作为吸附剂,进行了吸附去除水中Cr3 的试验.研究了溶液pH值、初始Cr3 浓度以及温度等因素对这2种吸附剂去除Cr3 作用的影响,对吸附曲线作了线性拟合,确定了相应的平衡吸附率,在Cr3 初始浓度为1、5、10和20 mg/L时,木屑对Cr3 的平衡吸附率为81%、68%、56%和40%,花生壳依次为77%、63%、53%和42%,并探讨了这2种吸附剂对溶液中Cr3 的吸附机理.     

Detoxification and repair process of ozone injury: from O3 uptake to gene expression adjustment

Plants react to O₃ threat by setting up a variety of defensive strategies involving the co-ordinated modulation of stress perception, signalling and metabolic responses. Although stomata largely controls O₃ uptake, differences in O₃ tolerance cannot always be ascribed to changes in stomatal conductance but cell protective and repair processes should be taken into account. O₃-driven ROS production in the apoplast induces a secondary, active, self-propagating generation of ROS, whose levels must be finely tuned, by many enzymatic and non-enzymatic antioxidant systems, to induce gene activation without determining uncontrolled cell death. Additional signalling molecules, as ethylene, jasmonic and salicylic acid are also crucial to determine the spreading and the containment of leaf lesions. The main recent results obtained on O₃ sensing, signal transduction, ROS formation and detoxification mechanisms are here discussed.     

EDTAD-modified cassava stalks loaded with Fe3O4: highly efficient removal of Pb2+ and Zn2+ from aqueous solution

Environmental Science and Pollution Research - In this study, a novel magnetic cassava stalk composite (M-EMCS) was prepared through modification with ethylenediamine tetraacetic anhydride (EDTAD)...     

Metal availability and uptake by sorghum plants grown in soils amended with sludge from different treatments

Several factors depending on the sludge, the soil, or the combination of both substrates, may affect element availability to plants. In this study, an assessment was done of the effect of two sludges obtained by different processes (activated sludge and facultative stabilization pond) on heavy-metal availability and uptake by sorghum plants in soils with high and low copper contents. Results obtained for DTPA-extractable metal indicated higher metal availability in sludge-amended soils. In addition, sludges caused changes in copper and zinc distribution in soil, indicating in most cases a discrete increase in the more labile metal forms. However, observed changes did not increase heavy metal concentration in plant leaves, indicating that assessment of metal availability by a chemical procedure (single extraction or metal fractionation) would not permit a good prediction of metal bioavailability. On the other hand, sludge application at a rate of 100 t ha⁻¹ to high-copper agricultural soils would not imply greater mobility of this metal on account of a greater sorbing capacity provided by the sludges. Such results would indicate that sludges from wastewater treatment plants, meeting the standards of heavy metal contents, regardless of the process by which they were obtained, may be applied to several kinds of soil, even to high-copper soils, with no risk of increasing heavy metal bioavailability to phytotoxic levels in the short range.     

The uptake of O3 by poplar leaves: the impact of a long-term exposure to low O3-concentrations

Poplar shoots were exposed for 3–4 weeks to filtered air, ambient (maximum values 50–60 nl ℓ^-1) or two times ambient O₃-concentrations under controlled environmental conditions in fumigation chambers. A sensitive (Populus nigra ‘Brandaris’) and a tolerant (P. euramericana ‘Robusta’) cultivar were used. At regular intervals the uptake of O₃, transpiration and CO₂ assimilation rate (P_n) of full-grown leaves were measured with leaf cuvettes. For unaffected leaves, the measured flux of O₃ into the leaves appeared to be larger than can be calculated using the stomatal conductance for O₃ (g_s,o) estimated from the transpiration rates of the same leaves. Resistance analysis revealed that the difference was partly a result of a reaction with the external leaf surface. However, when the O₃ flux into the leaf was corrected for this reaction, it was still larger than can be estimated using g_s,o. As a consequence, negative residual or internal resistances (r_i) for O₃ transport into the leaves were assessed. It is postulated that O₃ molecules moving into the leaf follow a shorter pathway than effluxing H₂O-molecules. P. ‘Brandaris’ leaves showed a reduction in P_n after 12 days of exposure to ambient O₃-concentrations, whereas for P. ‘Robusta’ a reduction in P_n was only observed at two times ambient concentrations. A simultaneous decline in the O₃-flux was found in both cases. The decline occurred before a decrease in g_s,o was observed suggesting that the O₃ flux into the affected leaves was first hindered by internal factors. The measured flux of the affected leaves became smaller than the flux estimated using g_s,o and, consequently, positive r_i-values were estimated. The change in r_i suggests that O₃ molecules not only penetrated deeper into the leaf, but also were accumulating at a prolonged exposure. Our results indicate that r_i may be a potentially important component of the overall resistance for O₃-uptake, which may have important consequences for estimating O₃ uptake from water vapour flux data.     

Formation of fine particles enriched by V and Ni from heavy oil combustion: Anthropogenic sources and drop-tube furnace experiments

The present study attempts to investigate the emission characteristics of fine particles with special emphasis on nickel and vanadium metal elements emitted from the heavy oil combustion in industrial boilers and power plant, which are typical anthropogenic sources in Korea. A series of combustion experiments were performed to investigate the emission characteristics of particles in the size range of submicron by means of drop-tube furnace with three major domestic heavy oils. Cascade impactors were utilized to determine the size distribution of particulates as well as to analyze the partitioning enrichment of vanadium and nickel in various size ranges. Experimental results were compared with field data of particle size distribution and metal partitioning at commercial utility boilers with heavy oil combustion. Such data were interpreted by chemical equilibrium and particle growth mechanism by means of computational models. In general, fine particles were the major portion of PM₁₀ emitted from the heavy oil combustion, with significant fraction of ultra-fine particles. The formation of ultra-fine particles through nucleation/condensation/coagulation from heavy oil combustion was confirmed by field and experimental data. Vanadium and nickel were more enriched in fine particles, particularly in ultra-fine particles. The conventional air pollution devices showed inefficient capability to remove ultra-fine particles enriched with hazardous transition metal elements such as vanadium and nickel.     

Nitrous oxide emission from an agricultural field: Comparison between measurements by flux chamber and micrometerological techniques

The soil in a drained fjord area, reclaimed for arable farming, produced N₂O mainly at 75–105 cm depth, just above the ground water level. Surface emissions of N₂O were measured from discrete small areas by closed and open-flow chamber methods, using gas chromatographic analysis and over larger areas by integrative methods: flux gradient (analysis by FTIR), conditional sampling (analysis by TDLAS), and eddy covariance (analysis by TDLAS). The mean emission of N₂O as determined by chamber procedures during a 9-day campaign was 162–202 μg N₂ONm⁻²h⁻¹ from a wheat stubble and 328–467 μg N₂ONm⁻² h⁻¹ from a carrot field. The integrative approaches gave N₂O emissions of 149–495 μg N₂ONm⁻² h⁻¹, i.e. a range similar to those determined with the chamber methods. Wind direction affected the comparison of chamber and integrative methods because of patchiness of the N₂O emission over the area. When a uniform area with a single type of vegetation had a dominant effect on the N₂O gradient at the sampling mast, the temporal variation in N₂O emission determined by the flux gradient/FTIR method and chamber methods was very similar, with differences of only 18% or less in mean N₂O emission, well below the variation encountered with the chamber methods themselves. A detailed comparison of FTIR gradient and chamber data taking into account the precise emission footprint showed good agreement. It is concluded that there was no bias between the different approaches used to measure the N₂O emission and that the precision of the measurements was determined by the spatial variability of the N₂O emission at the site and the variability inherent in the individual techniques. These results confirm that measurements of N₂O emissions from different ecosystems obtained by the different methods can be meaningfully compared.     

Reduction in uptake by rice and soybean of aromatic arsenicals from diphenylarsinic acid contaminated soil amended with activated charcoal

Activated charcoal (AC) amendment has been suggested as a promising method to immobilize organic contaminants in soil. We performed pot experiments with rice and soybean grown in agricultural soil polluted by aromatic arsenicals (AAs). The most abundant AA in rice grains and soybean seeds was methylphenylarsinic acid (MPAA). MPAA concentration in rice grains was significantly reduced to 2% and 3% in 0.2% AC treated soil compared to untreated soil in the first year of rice cultivation. In the second year, MPAA concentration in rice grains was significantly reduced to 15% in 0.2% AC treated soil compared to untreated soil. MPAA concentration in soybean seeds was significantly reduced to 44% in 0.2% AC treated soil compared to untreated soil. AC amendment was effective in reducing AAs in rice and soybean.     

Atmospheric oxalic acid and SOA production from glyoxal: Results of aqueous photooxidation experiments

Aqueous-phase photooxidation of glyoxal, a ubiquitous water-soluble gas-phase oxidation product of many compounds, is a potentially important global and regional source of oxalic acid and secondary organic aerosol (SOA). Reaction kinetics and product analysis are needed to validate and refine current aqueous-phase mechanisms to facilitate prediction of in-cloud oxalic acid and SOA formation from glyoxal. In this work, aqueous-phase photochemical reactions of glyoxal and hydrogen peroxide were conducted at pH values typical of clouds and fogs (i.e., pH=4–5). Experimental time series concentrations were compared to values obtained using a published kinetic model and reaction rate constants from the literature. Experimental results demonstrate the formation of oxalic acid, as predicted by the published aqueous phase mechanism. However, the published mechanism did not reproduce the glyoxylic and oxalic acid concentration dynamics. Formic acid and larger multifunctional compounds, which were not previously predicted, were also formed. An expanded aqueous-phase oxidation mechanism for glyoxal is proposed that reasonably explains the concentration dynamics of formic and oxalic acids and includes larger multifunctional compounds. The coefficient of determination for oxalic acid prediction was improved from 0.001 to >0.8 using the expanded mechanism. The model predicts that less than 1% of oxalic acid is formed through the glyoxylic acid pathway. This work supports the hypothesis that SOA forms through cloud processing of glyoxal and other water-soluble products of alkenes and aromatics of anthropogenic, biogenic and marine origin and provides reaction kinetics needed for oxalic acid prediction.     

Adsorption and desorption of 2,4,6-trichlorophenol onto and from ash as affected by Ag+, Zn2+, and Al3+

Metal cations and organic pollutants mostly co-exist in the natural environment. However, their interactions in adsorption processes have yet to be adequately addressed. In the current study, the effect of inorganic cations with different charges (Ag⁺, Zn²⁺, and Al³⁺) on the adsorption and desorption of 2,4,6-trichlorophenol (TCP) onto and from processed ash derived from wheat (Triticum aestivum L.) straw was investigated. The adsorption and desorption of TCP were both nonlinear; the isotherm and kinetics curves fitted well using the Freundlich equation and a pseudo-second-order model, respectively. The presence of Ag⁺ promoted TCP adsorption, while Zn²⁺ and Al³⁺ reduced TCP adsorption onto ash. The desorption of TCP from ash showed obvious hysteresis, and the presence of Ag⁺, Zn²⁺, and Al³⁺ caused the desorption to be less hysteretic. The suppression of TCP adsorption by Zn²⁺ and Al³⁺ was ascribed to the partial overlapping of adsorption groups between TCP and metal ions. Al³⁺ had a stronger inhibition effect than that of Zn²⁺ due to its higher binding capacity and larger hydrated ionic radius than those of Zn²⁺. Enhanced adsorption of TCP onto ash by Ag⁺ was ascribed to its ability to reduce the competitive adsorption of water molecules on ash surface by replacing the original ions, such as Na⁺ and Ca²⁺, and compressing the hydrated ionic radius of these metal ions. In addition, Ag⁺ was able to bind with the aromatic organic compounds containing π-electrons, which resulted in a further increase of TCP adsorption by ash.     

Comparison of techniques for estimating PAH bioavailability: uptake in Eisenia fetida, passive samplers and leaching using various solvents and additives

The aim of this study was to evaluate different techniques for assessing the availability of polycyclic aromatic hydrocarbons (PAHs) in soil. This was done by comparing the amounts (total and relative) taken up by the earthworm Eisenia fetida with the amounts extracted by solid-phase microextraction (SPME), semi-permeable membrane devices (SPMDs), leaching with various solvent mixtures, leaching using additives, and sequential leaching. Bioconcentration factors of PAHs in the earthworms based on equilibrium partitioning theory resulted in poor correlations to observed values. This was most notable for PAHs with high concentrations in the studied soil. Evaluation by principal component analysis (PCA) showed distinct differences between the evaluated techniques and, generally, there were larger proportions of carcinogenic PAHs (4-6 fused rings) in the earthworms. These results suggest that it may be difficult to develop a chemical method that is capable of mimicking biological uptake, and thus estimating the bioavailability of PAHs.     

Metal ion uptake from aqueous solution by olive stones: a carbon-13 solid-state nuclear magnetic resonance and potentiometric study.

The use of biomasses that result from the agriculture and food industries in removing heavy metals from wastewaters is attracting increasing interest. We present a joined potentiometric and cross polarization magic angle spinning (CP-MAS) carbon-13 (13C) nuclear magnetic resonance (NMR) study on the interaction of olive stones with copper(II), nickel(II), and cadmium(II). The potentiometric measurements allow both to distinguish two kind of basic sites in the olive stones and to postulate the coordination models for the three studied metals. The NMR spectral analysis allows the attribution of the different signals to the components of the olive stone matrix. A comparison of CP-MAS 13C NMR spectra of the samples after metal treatment suggests a specific complexation between metal ions and hydroxyl groups on guaiacyl and syringyl moieties.     

Effective uptake of decontaminating agent (citric acid) from aqueous solution by mesoporous and microporous materials: an adsorption process

The presence of citric acid in decontamination waste can cause complexation of the radioactive cations resulting in interferences in their removal by various treatment processes such as chemical precipitation, ion-exchange, etc., which are employed for the removal of radioactivity and may cause potential danger to the environment. Mesoporous Al-MCM-41 (Si/Al=30, 51, 72 and 97) and Si-MCM-41 molecular sieves were synthesized hydrothermally and characterized by XRD, BET (surface area) and FT-IR to evaluate the removal of citric acid through an adsorption process. Adsorption of citric acid over Al-MCM-41 shows the applicability of Freundlich and Langmuir isotherm and follows first order kinetics. The effects of contact time, concentration of citric acid, adsorbents (various Si/Al ratios of Al-MCM-41, Si-MCM-41, Hbeta zeolite and commercial carbon) and pH have been investigated. It has been found that the amount of citric acid adsorbed per unit gram of catalyst followed the order Al-MCM-41 (Si/Al=30)>Al-MCM-41 (Si/Al=51)>activated charcoal>Al-MCM-41 (Si/Al=72)>Al-MCM-41 (Si/Al=97)>Si-MCM-41>Hbeta zeolite.     

纳米级天然黄铁矿去除水中Cr6+,Cd2+和Pb2+

利用机械球磨的方法可以提高天然黄铁矿的活性,通过XRD和TEM对机械球磨后黄铁矿粉末的表面形态和物理性质进行表征。通过批实验的方法探讨在不同的pH,不同的球磨黄铁矿用量,不同的反应时间和温度的条件下黄铁矿对Cr6+,Cd2+和Pb2+的去除效果。研究结果表明,金属离子的吸收受到pH的影响,随着pH的升高,3种金属离子的吸附趋势出现了很大的不同。并且在分析pH对反应效果的影响时,需要考虑金属生成沉淀时的pH。同时,随着反应时间和温度的增加,3种金属离子的吸收量都有不同程度的升高。通过实验比较,球磨黄铁矿对Cr6+,Cd2+和Pb2+的去除能力大小为Pb2+ > Cr6+ > Cd2+。纳米级黄铁矿与Cr6+,Cd2+和Pb2+的反应过程符合准二级动力学方程。     

Fixed-bed study for lanthanide (La, Eu, Yb) ions removal from aqueous solutions by immobilized Pseudomonas aeruginosa: experimental data and modelization

A fixed-bed study was carried out by using cells of Pseudomonas aeruginosa immobilized in polyacrylamide gel as a biosorbent for the removal of lanthanide (La, Eu, Yb) ions from aqueous solutions. The effects of superficial liquid velocity based on empty column, particle size, influent concentration and bed depth on the lanthanum breakthrough curves were investigated. Immobilized biomass effectively removed lanthanum from a 6 mM solution with a maximum adsorption capacity of 342 micromolg(-1) (+/-10%) corresponding closely to that observed in earlier batch studies with free bacterial cells. The Bohart and Adams sorption model was employed to determine characteristic parameters useful for process design. Results indicated that the immobilized cells of P. aeruginosa enable removal of lanthanum, europium and ytterbium ions from aqueous effluents with significant and similar maximum adsorption capacities. Experiments with a mixed cation solution showed that the sequence of preferential biosorption was Eu3+ > or = Yb3+ > La3+. Around 96+/-4% of the bound lanthanum was desorbed from the column and concentrated by eluting with a 0.1 M EDTA solution. The feasibility of regenerating and reusing the biomass through three adsorption/desorption cycles was suggested. Neural networks were used to model breakthrough curves performed in the dynamic process. The ability of this statistical tool to predict the breakthrough times was discussed.     

90Sr uptake by Pinus ponderosa and Pinus radiata seedlings inoculated with ectomycorrhizal fungi

Strontium-90 ((90)Sr) is a radionuclide characteristic of fallout from nuclear reactor accidents and nuclear weapons testing. Prior studies have shown that Pinus ponderosa and P. radiata seedlings can remove appreciable quantities of (90)Sr from soil and store it in plant tissue. In this study, we inoculated P. ponderosa and P. radiata seedlings with one of five isolates of ectomycorrhizal fungi. Inoculated and noninoculated (control) seedlings were compared for their ability to remove (90)Sr from an organic growth medium. Seedlings were grown in a growth chamber in glass tubes containing 165 cm(3) of sphagnum peat moss and perlite (1 : 1 (v/v)) and, except in the controls, the fungal inoculum. After 3 months, 5978 Bq of (90)Sr in 1 ml of sterile, distilled, deionized water was added. Seedlings were grown for an additional month and then harvested. P. ponderosa seedlings with ectomycorrhizae accumulated 3.0-6.0% of the (90)Sr; bioconcentration ratios (Bq (90)Sr cm(-3) plant tissue/Bq (90)Sr cm(-3) growth medium) ranged from 98-162. Ectomycorrhizal P. radiata seedlings accumulated 6.0-6.9% of the (90)Sr; bioconcentration ratios ranged from 88-133. Nonmycorrhizal P. ponderosa and P. radiata seedlings accumulated only 0.6 and 0.7% of the (90)Sr and had bioconcentration ratios of 28 and 27, respectively. Ectomycorrhizal P. ponderosa and P. radiata seedlings are able to remove 3-5 times more (90)Sr from contaminated soil than seedlings without ectomycorrhizae.     

Bioavailability of PCBs from field-collected sediments: application of Tenax extraction and matrix-SPME techniques

Two chemical approaches, Tenax extraction and matrix solid phase microextraction (matrix-SPME), were evaluated for their potential to improve the prediction of bioavailability by equilibrium partitioning theory (EPT) across sediments with various characteristics. Biota-sediment accumulation factors (BSAFs) and body residues were quantified by exposing Lumbriculus variegatus to three PCB-contaminated field sediments. The concentration of PCBs in biota was positively correlated to the total PCB sediment concentration, the PCB concentration in the rapidly desorbing fraction estimated using Tenax extraction, and the PCB concentration on the SPME fibers. Results showed EPT was acceptable for estimating bioavailability from the tested sediments with sum PCB BSAFs of 1.18-2.47; however, it overestimated PCB bioavailability from sandy sediment. Both Tenax extraction and matrix-SPME, which take sequestration into account, reduced variability in prediction of PCB bioavailability across sediments, including the sandy sediment, and could be used as cost- and time-efficient alternatives for bioassay. Matrix-SPME was considered the better technique due to its ability to directly predict PCB body residues in the exposed biota and its potential use with in situ applications in the field.