Molecular-Scale Investigation on the Formation of Brown Carbon Aerosol via Iron-Phenolic Compound Reactions in the Dark.

Brown carbon (BrC) is one of the most mysterious aerosol components responsible for global warming and air pollution. Iron (Fe)-induced catalytic oxidation of ubiquitous phenolic compounds has been considered as a potential pathway for BrC formation in the dark. However, the reaction mechanism and product composition are still poorly understood. Herein, 13 phenolic precursors were employed to react with Fe under environmentally relevant conditions. Using Fourier transform ion cyclotron resonance mass spectrometry, a total of 764 unique molecular formulas were identified, and over 85% of them can be found in atmospheric aerosols. In particular, products derived from precursors with catechol-, guaiacol-, and syringol-like-based structures can be distinguished by their optical and molecular characteristics, indicating the structure-dependent formation of BrC from phenolic precursors. Multiple pieces of evidence indicate that under acidic conditions, the contribution of either autoxidation or oxygen-induced free radical oxidation to BrC formation is extremely limited. Ligand-to-Fe charge transfer and subsequent phenoxy radical coupling reactions were the main mechanism for the formation of polymerization products with high molecular diversity, and the efficiency of BrC generation was linearly correlated with the ionization potential of phenolic precursors. The present study uncovered how chemically diverse BrC products were formed by the Fe-phenolic compound reactions at the molecular level and also provide a new paradigm for the study of the atmospheric aerosol formation mechanism.

Main chemical and mineralogical components of the Rio Doce sediments and the iron ore tailing from the Fundão Dam disaster, Southeastern Brazil.

Since the Fundão Dam rupture in Southeastern Brazil caused an enormous amount of iron ore tailing (IOT) to be discharged into the Doce River Catchment, various works have been published on the soil, water, and biota contamination by potentially hazardous trace metals. However, the objective of this study is to investigate changes in the main chemical composition and the mineral phases, which has not been studied yet. We present an analysis of sediment samples collected in the Doce River alluvial plain, before and after the disaster, as well as the tailing deposited. Granulometry, main chemical composition by X-ray fluorescence spectrometry, mineralogy by X-ray diffractometry, quantification of mineral phases using the Rietveld method, and scanning electron microscope imaging are shown. We conclude that the Fundão Dam rupture introduced fine particles into the Doce River alluvial plain, increasing the Fe and Al content in the sediments. The high Fe, Al, and Mn contents in the finer iron ore tailing fractions represent environmental risks for soil, water, and biotic chains. The IOT mineralogical components, mainly the muscovite, kaolinite, and hematite present in the finer particles can increase the sorption and desorption capacity of harmful trace metals depending on the natural or induced redox conditions, which are not always predictable and avoidable in the environment.

Common and rare iron, sulfur, and zinc minerals in technogenically contaminated hydromorphic soil from Southern Russia.

Soils formed after the desiccation of Lake Atamanskoe, which has served as a reservoir for liquid industrial waste from the city of Kamensk-Shakhtinsky during a long time, were studied. These soils differ from zonal soils by a strong contamination with zinc and sulfur. Preliminary studies showed that Fe compounds fix a significant part of zinc. This requires to study S, Zn, and Fe minerals. In this work, Mössbauer spectroscopy was used for the identification of iron compounds and scanning electron microscopy was used for the microanalysis of these and other minerals. To facilitate the identification of Fe minerals, brown iron ocher was removed from a contaminated soil sample and analyzed. From electron microscopy and Mössbauer spectroscopy data, ocher contained hydrogoethite with a high content of sorption water and schwertmannite (a rare mineral, probably found in Russia for the first time). The chemical composition of this schwertmannite better corresponds to the Cashion-Murad model than to the Bigham model. Particles of partially oxidized magnetite and wustite enriched with zinc were revealed under electron microscope. Siderite with partial substitution of Fe2+ by Zn2+ was detected. Thus, contaminated hydromorphic soil contains both common minerals (illite, goethite, hematite, gypsum) and rare minerals (schwertmannite, Zn siderite, partially oxidized magnetite and wustite enriched with zinc).

A laboratory investigation on the performance of South African acid producing gold mine tailings and its possible use in mine reclamation.

This paper presents the results of laboratory investigations conducted on gold mine tailings (GMT) to assess their chemical, mineralogical and geotechnical characteristics in view of assessing its suitability as an alternative backfilling solution in mine reclamation. Chemical characterization revealed that GMT is dominated by Si, Al, and Fe with notable amounts of Cr, Zr, Zn, Pb, Ce, As, Ba, Ni, V, Sr, Nd, Cu, U, and Co. Mineralogical characterization revealed a composition of silicate minerals with secondary minerals such as jarosite, goethite and hematite. GMT composites showed improved strength characteristics. The particle sizes of the tailings are capable of producing a good paste fill that will require lower water-cement ratio. Moreover, the plasticity of the tailings provide for a likelihood for shear resistance to sliding in fluvial conditions. Curing and addition of cement showed positive effects on the compressive strength and shear strength of the tailings. However, the effect of curing and cement addition on the compaction characteristics and permeability of the tailings were negligible. GMT showed favorable characteristics for use in mine backfilling; it would be interesting to evaluate higher cement ratios to improve the characteristics of the tailings.

Detection of the iron complexes with hydrolysis products of cephalexin and cefradine upon high-performance liquid chromatography/electrospray ionization mass spectrometry analysis.

RATIONALE: Cephalosporins (e.g. cephalexin, cefradine) are a major group of widely used ß-lactam antibiotics. Hydrolysis of the ß-lactam ring is an important reaction (often undesired) which leads to deactivation of ß-lactams. To the best of our knowledge there is no electrospray ionization mass spectrometry (ESI-MS) data reported concerning the products of hydrolysis of cephalosporins. METHODS: The hydrolysis of cephalexin and cefradine was performed in aqueous NaOH solutions. After the process the solutions were analyzed by high-performance liquid chromatography (HPLC)/ESI-MS. The elemental compositions of the ions discussed were confirmed by the accurate mass measurements on a quadrupole time-of-flight (QTOF) mass spectrometer. RESULTS: Unexpectedly, complexes between the hydrolysis products of cephalexin and cefradine (CFLh and CFRh ) and iron cation were detected upon HPLC/ESI-MS analysis, namely the ions [(CFLh -H)2 +Fe]+ and [(CFRh -H)2 +Fe]+ , although iron was not added to the analyzed solutions or to the mobile phase. These ions were found to be very stable in the gas phase. CONCLUSIONS: The detection of the complexes between the hydrolysis products of cephalosporins and iron may have a positive impact on the sensitivity and specificity of HPLC/ESI-MS analyses of the hydrolysis products of some cephalosporins.

Migration and fate of metallic elements in a waste mud impoundment and affected river downstream: A case study in Dabaoshan Mine, South China.

Fate of metallic elements and their migration mechanisms in a waste mud impoundment and affected downstream were assessed. Physicochemical and mineralogical methods combined with PHREEQC calculation, statistical analysis and review of relevant literatures were employed. Results showed that the waste in mud impoundment had been severely weathered and acidized. Metallic elements exhibited high mobility and activity, with a mobility ranking order of Cd > Zn > Mn > Cu ≈ Cr > As ≈ Pb. Hydraulic transportation originating from elevation variation was the most important driving force for metallic elements migration. Although damming standstill was considered as an effective strategy for controlling coarse suspended particulate pollutants, metallic elements were still transported to the Hengshi River in both dissolved phase and fine suspended particle phase accompanied by the overflow of acid mine drainage. The concentrations of dissolved metallic elements were attenuated significantly along the Hengshi River within 41 km stretch. Precipitation/ co-precipitation of iron oxyhydroxides, especially schwertmannite, ferrihydrite and goethite minerals, were established as the most critical processes for metallic elements attenuation in river water. Accompanied by metals migration in the river, two pollution sensitive sites with notably high content of metals in the stretch of S6-S8 and S10, were identified in gently sloping river stretch.

Characteristics and environmental response of secondary minerals in AMD from Dabaoshan Mine, South China.

This article documents the new precipitates formed related to acid mine drainage (AMD) at Dabaoshan mine (South China). X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscope & Energy Spectrometer (SEM-EDS) have been used to detect minerals in AMD impoundment and downstream creeks. The occurrences, the mineralogical species and the micro-morphological characteristics of secondary minerals from different pH conditions has been carried out. Iron- hydroxysulfates and iron-oxyhydroxides are the main secondary minerals, and they occurred as both poorly and well-crystalline minerals. Jarosite nearly predominate as pseudocubic crystals at pH 2.5-4.0. Schwertmannite-rich sediments occurred at pH 3.82-4.5 as urchin-like, pin-cushion and as well as globular-like aggregates and show high concentrations of Mn, Cu, Pb and As due to adsorption and co-precipitation. Goethite formed mainly as botryoidal and flaky assemblages. Paragenesis of different types of schwertmannite indicate that pH condition is not the dominant factor controlling morphology but the main parameter for the variation of minerals species. Statistical analysis reveal obvious changing tendency in Zn, Cd and SO4 within pH. FTIR analysis show adsorption of Cu, Pb, Zn and As on secondary iron minerals. Water elements with high concentrations in the impoundment and the obvious decrease in downstream creak reflected an accumulation and evaporation in AMD impoundment and a dilution in downstream area respectively. These results indicate that secondary minerals associated with AMD can play an important role in attenuating toxic elements.

Improved ciprofloxacin removal by a Fe(VI)-Fe3O4/graphene system under visible light irradiation.

In this paper, Fe3O4/graphene (Fe3O4/GE) nanocomposites were prepared by a co-precipitation method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and UV-vis diffuse reflectance spectra (UV-vis DRS). The composites were used in combination with Fe(VI) to construct a Fe(VI)-Fe3O4/GE system in order to degrade ciprofloxacin (CIP) in simulated water samples. The photocatalytic properties of Fe(VI)-Fe3O4/GE were evaluated under visible light irradiation. The concentration of CIP in solution was detected by high performance liquid chromatography (HPLC). A series of results showed that Fe(VI), as a good electron capture agent, could significantly improve the treatment performance. Major determining factors during CIP degradation were also investigated, in which solution pH of 9, Fe(VI) to Fe3O4/GE dosage ratio of 1:25 and GE content in the Fe3O4/GE nanocomposites of 10 wt% were found to be the best experimental conditions. The results demonstrated that the Fe(VI)-Fe3O4/GE system could offer an alternative process in water treatment in addition to the current Fe(VI)-UV/TiO2 process.

Deciphering the Complex Chemistry of Deep-Ocean Particles Using Complementary Synchrotron X-ray Microscope and Microprobe Instruments.

The reactivity and mobility of natural particles in aquatic systems have wide ranging implications for the functioning of Earth surface systems. Particles in the ocean are biologically and chemically reactive, mobile, and complex in composition. The chemical composition of marine particles is thought to be central to understanding processes that convert globally relevant elements, such as C and Fe, among forms with varying bioavailability and mobility in the ocean. The analytical tools needed to measure the complex chemistry of natural particles are the subject of this Account. We describe how a suite of complementary synchrotron radiation instruments with nano- and micrometer focusing, and X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) capabilities are changing our understanding of deep-ocean chemistry and life. Submarine venting along mid-ocean ridges creates hydrothermal plumes where dynamic particle-forming reactions occur as vent fluids mix with deep-ocean waters. Whether plumes are net sources or sinks of elements in ocean budgets depends in large part on particle formation, reactivity, and transport properties. Hydrothermal plume particles have been shown to host microbial communities and exhibit complex size distributions, aggregation behavior, and composition. X-ray microscope and microprobe instruments can address particle size and aggregation, but their true strength is in measuring chemical composition. Plume particles comprise a stunning array of inorganic and organic phases, from single-crystal sulfides to poorly ordered nanophases and polymeric organic matrices to microbial cells. X-ray microscopes and X-ray microprobes with elemental imaging, XAS, and XRD capabilities are ideal for investigating these complex materials because they can (1) measure the chemistry of organic and inorganic constituents in complex matrices, usually within the same particle or aggregate, (2) provide strong signal-to-noise data with exceedingly small amounts of material, (3) simplify the chemical complexity of particles or sets of particles with a focused-beam, providing spatial resolution over 6 orders of magnitude (nanometer to millimeter), (4) provide elemental specificity for elements in the soft-, tender-, and hard-X-ray energies, (5) switch rapidly among elements of interest, and (6) function in the presence of water and gases. Synchrotron derived data sets are discussed in the context of important advances in deep-ocean technology, sample handling and preservation, molecular microbiology, and coupled physical-chemical-biological modeling. Particle chemistry, size, and morphology are all important in determining whether particles are reactive with dissolved constituents, provide substrates for microbial respiration and growth, and are delivered to marine sediments or dispersed by deep-ocean currents.

Discovery and Characterization of Iron Sulfide and Polyphosphate Bodies Coexisting in Archaeoglobus fulgidus Cells.

Inorganic storage granules have long been recognized in bacterial and eukaryotic cells but were only recently identified in archaeal cells. Here, we report the cellular organization and chemical compositions of storage granules in the Euryarchaeon, Archaeoglobus fulgidus strain VC16, a hyperthermophilic, anaerobic, and sulfate-reducing microorganism. Dense granules were apparent in A. fulgidus cells imaged by cryo electron microscopy (cryoEM) but not so by negative stain electron microscopy. Cryo electron tomography (cryoET) revealed that each cell contains one to several dense granules located near the cell membrane. Energy dispersive X-ray (EDX) spectroscopy and scanning transmission electron microscopy (STEM) show that, surprisingly, each cell contains not just one but often two types of granules with different elemental compositions. One type, named iron sulfide body (ISB), is composed mainly of the elements iron and sulfur plus copper; and the other one, called polyphosphate body (PPB), is composed of phosphorus and oxygen plus magnesium, calcium, and aluminum. PPBs are likely used for energy storage and/or metal sequestration/detoxification. ISBs could result from the reduction of sulfate to sulfide via anaerobic energy harvesting pathways and may be associated with energy and/or metal storage or detoxification. The exceptional ability of these archaeal cells to sequester different elements may have novel bioengineering applications.

Leaching characteristics of encapsulated controlled low-strength materials containing arsenic-bearing waste precipitates from refractory gold bioleaching.

We report on the leaching of heavy elements from cemented waste flowable fill, known as controlled low-strength materials (CLSM), for potential mine backfill application. Semi-dynamic tank leaching tests were carried out on laboratory-scale monoliths cured for 28 days and tested over 64 days of leaching with pure de-ionised water as leachant. Mineral processing waste include flotation tailings from a Spanish nickel-copper sulphide concentrate, and two bioleach neutralisation precipitates (from processing at 35°C and 70°C) from a South African arsenopyrite concentrate. Encapsulated CLSM formulations were evaluated to assess the reduction in leaching by encapsulating a 'hazardous' CLSM core within a layer of relatively 'inert' CLSM. The effect of each bioleach waste in CLSM core and tailings in CLSM encapsulating medium, are assessed in combination and in addition to CLSM with ordinary silica sand. Results show that replacing silica sand with tailings, both as core and encapsulating matrix, significantly reduced leachability of heavy elements, particularly As (from 0.008-0.190 mg/l to 0.008-0.060 mg/l), Ba (from 0.435-1.540 mg/l to 0.050-0.565 mg/l), and Cr (from 0.006-0.458 mg/l to 0.004-0.229 mg/l), to below the 'Dutch List' of groundwater contamination intervention values. Arsenic leaching was inherently high from both bioleach precipitates but was significantly reduced to below guideline values with encapsulation and replacing silica sand with tailings. Tailings proved to be a valuable encapsulating matrix largely owing to small particle size and lower hydraulic conductivity reducing diffusion transport of heavy elements. Field-scale trials would be necessary to prove this concept of encapsulation in terms of scale and construction practicalities, and further geochemical investigation to optimise leaching performance. Nevertheless, this work substantiates the need for alternative backfill techniques for sustainable management of hazardous finely-sized bulk mineral residues.

Stable isotopes and iron oxide mineral products as markers of chemodenitrification.

When oxygen is limiting in soils and sediments, microorganisms utilize nitrate (NO3-) in respiration--through the process of denitrification--leading to the production of dinitrogen (N2) gas and trace amounts of nitrous (N2O) and nitric (NO) oxides. A chemical pathway involving reaction of ferrous iron (Fe2+) with nitrite (NO2-), an intermediate in the denitrification pathway, can also result in production of N2O. We examine the chemical reduction of NO2- by Fe(II)--chemodenitrification--in anoxic batch incubations at neutral pH. Aqueous Fe2+ and NO2- reacted rapidly, producing N2O and generating Fe(III) (hydr)oxide mineral products. Lepidocrotite and goethite, identified by synchrotron X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy, were produced from initially aqueous reactants, with two-line ferrihydrite increasing in abundance later in the reaction sequence. Based on the similarity of apparent rate constants with different mineral catalysts, we propose that the chemodenitrification rate is insensitive to the type of Fe(III) (hydr)oxide. With stable isotope measurements, we reveal a narrow range of isotopic fractionation during NO2- reduction to N2O. The location of N isotopes in the linear N2O molecule, known as site preference, was also constrained to a signature range. The coexistence of Fe(III) (hydr)oxide, characteristic 15N and 18O fractionation, and N2O site preference may be used in combination to qualitatively distinguish between abiotic and biogenically emitted N2O--a finding important for determining N2O sources in natural systems.

Coexistence of Cu, Fe, Pb, and Zn oxides and chlorides as a determinant of chlorinated aromatics generation in municipal solid waste incinerator fly ash.

We investigated chemical determinants of the generation of chlorinated aromatic compounds (aromatic-Cls), such as polychlorinated biphenyls (PCBs) and chlorobenzenes (CBzs), in fly ash from municipal solid waste incineration. The influences of the following on aromatic-Cls formation in model fly ash (MFA) were systematically examined quantitatively and statistically: (i) inorganic chlorides (KCl, NaCl, CaCl2), (ii) base materials (SiO2, Al2O3, CaCO3), (iii) metal oxides (CuO, Fe2O3, PbO, ZnO), (iv) metal chlorides (CuCl2, FeCl3, PbCl2, ZnCl2), and (v) "coexisting multi-models." On the basis of aromatic-Cls concentrations, the ∑CBzs/∑PCBs ratio, and the similarity between distribution patterns, MFAs were categorized into six groups. The results and analysis indicated that the formation of aromatic-Cls depended strongly on the "coexistence condition", namely multimodels composed of not only metal chlorides, but also of metal oxides. The precise replication of metal chloride to oxide ratios, such as the precise ratios of Cu-, Fe-, Pb-, and Zn-chlorides and oxides, may be an essential factor in changing the thermochemical formation patterns of aromatic-Cls. Although CuCl2 acted as a promoter of aromatic-Cls generation, statistical analyses implied that FeCl3 also largely influenced the generation of aromatic-Cls under mixture conditions. Various additional components of fly ash were also comprehensively analyzed.

Speciation of radioactive soil particles in the Fukushima contaminated area by IP autoradiography and microanalyses.

Radioactive soil particles several tens of micrometers in size were collected from litter soil in the radiation contaminated area by the Fukushima nuclear plant accident and characterized using electron and X-ray microanalyses. The radioactive particles were discriminated by autoradiography using imaging plates (IP) on which microgrids were formed by laser ablation in order to find the particles under microscopy. Fifty radioactive particles were identified and classified into three types from their morphology and chemical composition, namely: (1) aggregates of clay minerals, (2) organic matter containing clay mineral particulates, and (3) weathered biotite originating from local granite. With respect to the second type, dissolution of the organic matter did not reduce the radiation, suggesting that the radionuclides were also fixed by the clay minerals. The weathered biotite grains have a plate-like shape with well-developed cleavages inside the grains, and kaolin group minerals and goethite filling the cleavage spaces. The reduction of the radiation intensity was measured before and after the trimming of the plate edges using a focused ion beam (FIB), to examine whether radioactive cesium primarily sorbed at frayed edges. The radiation was attenuated in proportion to the volume decrease by the edge trimming, implying that radioactive cesium was sorbed uniformly in the porous weathered biotite.

Water chemistry impacts on arsenic mobilization from arsenopyrite dissolution and secondary mineral precipitation: implications for managed aquifer recharge.

Managed aquifer recharge (MAR) is a water reuse technique with the potential to meet growing water demands. However, MAR sites have encountered arsenic mobilization resulting from recharge operations. To combat this challenge, it is imperative to identify the mechanisms of arsenic mobilization during MAR. In this bench-scale study, arsenic mobilization from arsenopyrite (FeAsS) was characterized for conditions relevant to MAR operations. Experimentally determined activation energies for arsenic mobilization from FeAsS under aerobic conditions were 36.9 ± 2.3 kJ/mol for 10 mM sodium chloride, 40.8 ± 3.5 kJ/mol for 10 mM sodium nitrate, and 43.6 ± 5.0 kJ/mol for secondary effluent from a wastewater treatment plant. Interestingly, the sodium chloride system showed higher arsenic mobilization under aerobic conditions. In addition, secondary mineral precipitation varied among systems and further affected arsenic mobilization. For example, the wastewater system inhibited precipitation, while in the sodium chloride system, faster phase transformation of iron(III) (hydr)oxide precipitates was observed, resulting in hematite formation after 7 days. The phase transformation to hematite will result in less available surface area for arsenic attenuation. These new observations and activation energies can be useful to develop improved reactive transport models for the fate of arsenic during MAR, and develop strategies to minimize arsenic release.

Enhanced carcinogenicity by coexposure to arsenic and iron and a novel remediation system for the elements in well drinking water.

Various carcinomas including skin cancer are explosively increasing in arsenicosis patients who drink arsenic-polluted well water, especially in Bangladesh. Although well drinking water in the cancer-prone areas contains various elements, very little is known about the effects of elements except arsenic on carcinogenicity. In order to clarify the carcinogenic effects of coexposure to arsenic and iron, anchorage-independent growth and invasion in human untransformed HaCaT and transformed A431 keratinocytes were examined. Since the mean ratio of arsenic and iron in well water was 1:10 in cancer-prone areas of Bangladesh, effects of 1 µM arsenic and 10 µM iron were investigated. Iron synergistically promoted arsenic-mediated anchorage-independent growth in untransformed and transformed keratinocytes. Iron additionally increased invasion in both types of keratinocytes. Activities of c-SRC and ERK that regulate anchorage-independent growth and invasion were synergistically enhanced in both types of keratinocytes. Our results suggest that iron promotes arsenic-mediated transformation of untransformed keratinocytes and progression of transformed keratinocytes. We then developed a low-cost and high-performance adsorbent composed of a hydrotalcite-like compound for arsenic and iron. The adsorbent rapidly reduced concentrations of both elements from well drinking water in cancer-prone areas of Bangladesh to levels less than those in WHO health-based guidelines for drinking water. Thus, we not only demonstrated for the first time increased carcinogenicity by coexposure to arsenic and iron but also proposed a novel remediation system for well drinking water.

Fortification of wheat flour and maize meal with different iron compounds: results of a series of baking trials.

BACKGROUND: Wheat and maize flour fortification is a preventive food-based approach to improve the micronutrient status of populations. In 2009, the World Health Organization (WHO) released recommendations for such fortification, with guidelines on the addition levels for iron, folic acid, vitamin B12, vitamin A, and zinc at various levels of average daily consumption. Iron is the micronutrient of greatest concern to the food industry, as some believe there may be some adverse interaction(s) in some or all of the finished products produced from wheat flour and maize meal. OBJECTIVE: To determine if there were any adverse interactions due to selection of iron compounds and, if differences were noted, to quantify those differences. METHODS: Wheat flour and maize meal were sourced in Kenya, South Africa, and Tanzania, and the iron compound (sodium iron ethylenediaminetetraacetate [NaFeEDTA], ferrous fumarate, or ferrous sulfate) was varied and dosed at rates according to the WHO guidelines for consumption of 75 to 149 g/day of wheat flour and > 300 g/day of maize meal and tested again for 150 to 300 g/day for both. Bread, chapatti, ugali (thick porridge), and uji (thin porridge) were prepared locally and assessed on whether the products were acceptable under industry-approved criteria and whether industry could discern any differences, knowing that differences existed, by academic sensory analysis using a combination of trained and untrained panelists and in direct side-by-side comparison. RESULTS: Industry (the wheat and maize milling sector) scored the samples as well above the minimal standard, and under academic scrutiny no differences were reported. Side-by-side comparison by the milling industry did indicate some slight differences, mainly with respect to color, although these differences did not correlate with any particular iron compound. CONCLUSIONS: The levels of iron compounds used, in accordance with the WHO guidelines, do not lead to changes in the baking and cooking properties of the wheat flour and maize meal. Respondents trained to measure against a set benchmark and/or discern differences could not consistently replicate perceived difference observations.

Recovery of iron oxides from acid mine drainage and their application as adsorbent or catalyst.

Iron oxide particles recovered from acid mine drainage represent a potential low-cost feedstock to replace reagent-grade chemicals in the production of goethite, ferrihydrite or magnetite with relatively high purity. Also, the properties of iron oxides recovered from acid mine drainage mean that they can be exploited as catalysts and/or adsorbents to remove azo dyes from aqueous solutions. The main aim of this study was to recover iron oxides with relatively high purity from acid mine drainage to act as a catalyst in the oxidation of dye through a Fenton-like mechanism or as an adsorbent to remove dyes from an aqueous solution. Iron oxides (goethite) were recovered from acid mine drainage through a sequential precipitation method. Thermal treatment at temperatures higher than 300 °C produces hematite through a decrease in the BET area and an increase in the point of zero charge. In the absence of hydrogen peroxide, the solids adsorbed the textile dye Procion Red H-E7B according to the Langmuir model, and the maximum amount adsorbed decreased as the temperature of the thermal treatment increased. The decomposition kinetics of hydrogen peroxide is dependent on the H(2)O(2) concentration and iron oxides dosage, but the second-order rate constant normalized to the BET surface area is similar to that for different iron oxides tested in this and others studies. These results indicate that acid mine drainage could be used as a source material for the production of iron oxide catalysts/adsorbents, with comparable quality to those produced using analytical-grade reagents.

Regulation of brain copper homeostasis by the brain barrier systems: effects of Fe-overload and Fe-deficiency.

Maintaining brain Cu homeostasis is vital for normal brain function. The role of systemic Fe deficiency (FeD) or overload (FeO) due to metabolic diseases or environmental insults in Cu homeostasis in the cerebrospinal fluid (CSF) and brain tissues remains unknown. This study was designed to investigate how blood-brain barrier (BBB) and blood-SCF barrier (BCB) regulated Cu transport and how FeO or FeD altered brain Cu homeostasis. Rats received an Fe-enriched or Fe-depleted diet for 4 weeks. FeD and FeO treatment resulted in a significant increase (+55%) and decrease (-56%) in CSF Cu levels (p<0.05), respectively; however, neither treatment had any effect on CSF Fe levels. The FeD, but not FeO, led to significant increases in Cu levels in brain parenchyma and the choroid plexus. In situ brain perfusion studies demonstrated that the rate of Cu transport into the brain parenchyma was significantly faster in FeD rats (+92%) and significantly slower (-53%) in FeO rats than in controls. In vitro two chamber Transwell transepithelial transport studies using primary choroidal epithelial cells revealed a predominant efflux of Cu from the CSF to blood compartment by the BCB. Further ventriculo-cisternal perfusion studies showed that Cu clearance by the choroid plexus in FeD animals was significantly greater than control (p<0.05). Taken together, our results demonstrate that both the BBB and BCB contribute to maintain a stable Cu homeostasis in the brain and CSF. Cu appears to enter the brain primarily via the BBB and is subsequently removed from the CSF by the BCB. FeD has a more profound effect on brain Cu levels than FeO. FeD increases Cu transport at the brain barriers and prompts Cu overload in the CNS. The BCB plays a key role in removing the excess Cu from the CSF.

Effects of Zwitterionic buffers on sorption of ferrous iron at goethite and its oxidation by CCl4.

A major factor which controls sorption and oxidation of Fe(II) at the mineral-water interface is pH, hence buffers are commonly used to control pH in experimental studies. Here, we examined the effects of widely used organic buffers (3-morpholinopropane-1-sulfonic acid (MOPS) and 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES)) on Fe(II) uptake and oxidation by CCl(4) in aqueous suspensions of goethite. Significant sorption of these zwitterionic buffers occurred only at Fe(II)-loaded goethite but not at native goethite. The addition of MOPS and HEPES caused substantial release of Fe(II) from goethite, retarded the oxidation of surface-bound Fe(II) by CCl(4) and changed the reaction pathway as indicated by lower yields of CHCl(3). To explore electrostatic and steric contributions of MOPS and HEPES to the observed phenomena we studied sorption and competitive effects of model sorbates (Ca(2+), sulfonates) which suggest the formation of a complex between surface-bound Fe(II) and MOPS or HEPES. Our study shows for the first time that these frequently used zwitterionic organic buffers may interfere significantly with the surface chemistry and thus with redox reactions of Fe(II) at goethite. Hence, kinetic or mechanistic information obtained in such systems requires careful interpretation.