The interaction of iron pyrite with oxygen, nitrogen and nitrogen oxides: a first-principles study

Sulphide materials, in particular MoS2, have recently received great attention from the surface science community due to their extraordinary catalytic properties. Interestingly, the chemical activity of iron pyrite (FeS2) (the most common sulphide mineral on Earth), and in particular its potential for catalytic applications, has not been investigated so thoroughly. In this study, we use density functional theory (DFT) to investigate the surface interactions of fundamental atmospheric components such as oxygen and nitrogen, and we have explored the adsorption and dissociation of nitrogen monoxide (NO) and nitrogen dioxide (NO2) on the FeS2(100) surface. Our results show that both those environmentally important NOx species chemisorb on the surface Fe sites, while the S sites are basically unreactive for all the molecular species considered in this study and even prevent NO2 adsorption onto one of the non-equivalent Fe–Fe bridge sites of the (1 1)–FeS2(100) surface. From the calculated high barrier for NO and NO2 direct dissociation on this surface, we can deduce that both nitrogen oxides species are adsorbed molecularly on pyrite surfaces.

Synthesis, characterisation and magnetic properties of a one-dimensional Iron(II) coordination polymer

A new iron(II) coordination polymer, [FeCl2(NC7H9)2(N2C12H12)], has been synthesized under solvothermal conditions and structurally characterized by single-crystal X-ray diffraction. This material crystallizes in the monoclinic space group C2/c, with a = 11.2850(6), b = 13.8925(7), c = 17.0988(9) Å and β = 94.300(3)º (Z = 4). The crystal structure consists of neutral zig-zag chains, in which the iron(II) ions are octahedrally coordinated. The infinite polymer chains are packed into a three-dimensional structure through C–H···Cl interactions. Magnetic susceptibility measurements reveal the existence of weak antiferromagnetic interactions between the iron(II) ions. The effective magnetic moment, μ eff = 5.33 μ B , is consistent with a high-spin iron(II) configuration.

Condiments before Claudius: new plant foods at the Late Iron Age oppidum at Silchester, UK

Our understanding of the introduction and adoption of new plant foods in Roman Britain is currently limited by a lack of data from a group of Late Iron Age settlements commonly referred to as oppida (large pre-Roman towns). This paper presents the first evidence of several imported plant foods from Late Iron Age Britain in the form of waterlogged plant remains from the oppidum at Silchester. These were recovered from the basal contexts of two wells, dated to the early first century a.d. One olive stone and several seeds of celery, coriander and dill were identified. The results are compared to archaeobotanical data from elsewhere in Britain and northwestern Europe, demonstrating that Silchester is part of the wider phenomenon of the adoption of new flavourings and fruits in Late Iron Age Europe.

Electronic structure of porphyrin-based metal-organic frameworks and their suitability for solar fuel production photocatalysis

Metal-organic frameworks (MOFs) can be exceptionally good catalytic materials thanks to the presence of active metal centres and a porous structure that is advantageous for molecular adsorption and confinement. We present here a first-principles investigation of the electronic structure of a family of MOFs based on porphyrins connected through phenyl-carboxyl ligands and AlOH species, in order to assess their suitability for the photocatalysis of fuel production reactions using sunlight. We consider structures with protonated porphyrins and those with the protons exchanged with late 3d metal cations (Fe2+, Co2+, Ni2+, Cu2+, Zn2+), a process that we find to be thermodynamically favorable from aqueous solution for all these metals. Our band structure calculations, based on an accurate screened hybrid functional, reveal that the bandgaps are in a favorable range (2.0 to 2.6 eV) for efficient adsorption of solar light. Furthermore, by approximating the vacuum level to the pore center potential, we provide the alignment of the MOFs’ band edges with the redox potentials for water splitting and carbon dioxide reduction, and show that the structures studied here have band edges positions suitable for these reactions at neutral pH.

Higher PUFA and omega-3 PUFA, CLA, α-tocopherol and iron, but lower iodine and selenium concentrations in organic milk: a systematic literature review and meta- and redundancy analyses

Demand for organic milk is partially driven by consumer perceptions that it is more nutritious. However, there is still considerable uncertainty over whether the use of organic production standards affects milk quality. Here we report results of meta-analyses based on 170 published studies comparing the nutrient content of organic and conventional bovine milk. There were no significant differences in total SFA and MUFA concentrations between organic and conventional milk. However, concentrations of total PUFA and n-3 PUFA were significantly higher in organic milk, by an estimated 7 (95 % CI −1, 15) % and 56 (95 % CI 38, 74) %, respectively. Concentrations of α-linolenic acid (ALA), very long-chain n-3 fatty acids (EPA+DPA+DHA) and conjugated linoleic acid were also significantly higher in organic milk, by an 69 (95 % CI 53, 84) %, 57 (95 % CI 27, 87) % and 41 (95 % CI 14, 68) %, respectively. As there were no significant differences in total n-6 PUFA and linoleic acid (LA) concentrations, the n-6:n-3 and LA:ALA ratios were lower in organic milk, by an estimated 71 (95 % CI −122, −20) % and 93 (95 % CI −116, −70) %. It is concluded that organic bovine milk has a more desirable fatty acid composition than conventional milk. Meta-analyses also showed that organic milk has significantly higher α-tocopherol and Fe, but lower I and Se concentrations. Redundancy analysis of data from a large cross-European milk quality survey indicates that the higher grazing/conserved forage intakes in organic systems were the main reason for milk composition differences.

Agricultural innovations at a Late Iron Age oppidum: archaeobotanical evidence for flax, food and fodder from Calleva Atrebatum, UK

The development of oppida in the late first millennium BC across north-western Europe represents a major change in settlement form and social organisation. The construction of extensive earthwork systems, the presence of nucleated settlement areas, long-distance trade links and the development of hierarchical societies have been evidenced. These imply that changes in the style and organisation of agriculture would have been required to support these proto-urban population centres. Hypotheses of the subsistence bases of these settlements, ranging from a reliance on surplus arable production from local rural settlements, to an emphasis on pastoral activities, are here reviewed and grounded against a wider understanding of the expansion of agriculture in the Late Iron Age. These agricultural models have not been previously evaluated. This paper presents archaeobotanical data from six well fills from large-scale excavations at Late Iron Age and Early Roman Silchester, a Late Iron Age territorial oppidum and subsequent Roman civitas capital located in central-southern Britain. This is the first large-scale study of waterlogged plant macrofossils from within a settlement area of an oppidum. Waterlogged plant macrofossils were studied from a series of wells within the settlement. An assessment of taphonomy, considering stratigraphic and contextual information, is reported, followed by an analysis of the diverse assemblages of the plant remains through univariate analysis. Key results evidence animal stabling, flax cultivation, hay meadow management and the use of heathland resources. The staple crops cultivated and consumed at Late Iron Age and Early Roman Silchester are consistent with those cultivated in the wider region, whilst a range of imported fruits and flavourings were also present. The adoption of new oil crops and new grassland management shows that agricultural innovations were associated with foddering for animals rather than providing food for the proto-urban population. The evidence from Silchester is compared with other archaeobotanical datasets from oppida in Europe in order to identify key trends in agricultural change.

Iron deficiency anaemia and blood lead concentrations in Brazilian children

This study investigated the relationship between iron deficiency/iron deficiency anaemia, assessed by several parameters, and blood lead concentration in children. This cross-sectional study involved 384 Brazilian children, aged 2-11 years, who lived near a lead-manipulating industry. Complete blood counts were obtained by an automated cell counter. Serum iron, total iron binding capacity (TIBC) and ferritin were determined respectively, by colorimetric, turbidimetric methods and chemiluminescence. Blood lead was measured by atomic absorption spectrophotometry. The impact of several parameters for assessment of iron status (haemoglobin, serum iron, TIBC, transferrin saturation, ferritin, red cell indices and red cell distribution width) and variables (gender, age, mother`s education, income, body mass index, iron intake, and distance from home to lead-manipulating industry) on blood lead concentration was determined by multiple linear regression. There were significant negative associations between blood lead and the distance from home to the lead-manipulating industry (P < 0.001), Hb (P = 0.019), and ferritin (P=0.023) (R(2)=0.14). Based on these results, further epidemiological studies are necessary to investigate the impact of interventions like iron supplementation or fortification, as an attempt to decrease blood lead in children. (C) 2011 Royal Society of Tropical Medicine and Hygiene. Published by Elsevier Ltd. All rights reserved.

Fortified food made by the extrusion of a mixture of chickpea, corn and bovine lung controls iron-deficiency anaemia in preschool children

A fortified food that was rich in protein, vitamins and iron made of chickpea, bovine lung and corn was developed with the aim of controlling iron-deficiency anaemia in children from poorer areas. It was tested in Teresina, State of Piaui, Northeastern Brazil, on a population with high anaemia prevalence. Two local daycare units with similar characteristics were selected and the children at one of them received a 30 g pack three times a week, representing a total iron daily intake of 6.96 mg. The other daycare unit was followed as a control. The capillary haemoglobin concentration was determined for the children at both daycare units, at the beginning of the study and after a two-month intervention period. The mean haemoglobin concentration in the test group at the beginning of the intervention was 11.8 g/dL, which increased to 13.1 g/dL at the end of the intervention. In the control group these figures remained practically constant (11.6-11.8 g/dL). These represented a dramatic and significant drop in anaemia prevalence, from 61.5% to 11.5% in the test group, and an insignificant reduction (63.1-57.7%) in the control group. The acceptance of the fortified snack was excellent and no undesirable effects were observed. (C) 2007 Published by Elsevier Ltd.

Iron Concentrations in Breast Milk and Selected Maternal Factors of Human Milk Bank Donors

The aim of this study was to evaluate the relationship between iron concentration in mature breast milk and characteristics of 136 donors of a Brazilian milk bank. Iron, vitamin A, zinc, and copper concentrations were assessed in human milk and maternal blood. Data were collected on maternal anthropometrics, obstetric, socioeconomic, demographic, and lifestyle factors. Iron, zinc, and copper in milk and zinc and copper in blood were detected by spectrophotometry. Vitamin A in milk and blood was determined by high-performance liquid chromatography. Hemoglobin was measured by electronic counting and serum iron and ferritin by colorimetry and chemoluminescence, respectively. Transferrin and ceruloplasmin were determined by nephelometry. According to multivariate linear regression analysis, iron in milk was positively associated with vitamin A in milk and with smoking but negatively associated with timing of breast milk donation (P < .001). These results indicate that iron concentration in milk of Brazilian donors may be influenced by nutritional factors and smoking. J Hum Lact. 26(2):175-179