Insight into the adsorption competition and the relationship between dissociation and association reactions in ammonia synthesis

Ammonia synthesis on three metal surfaces (Zr, Ru, and Pd) is investigated using density functional theory calculations. In addition to N-2 dissociation, all the transition states of the hydrogenation reactions from N to NH3 are located and the reaction energy profiles at both low and high surface coverages are compared and analyzed. The following are found: (i) Surface coverage effect on dissociation reactions is more significant than that on association reactions. (ii) The difference between N and H chemisorption energies, the so-called chemisorption energy gap which is a measure of adsorption competition, is vital to the reactivity of the catalysts. (iii) The hydrogenation barriers can considerably affect the overall rate of ammonia synthesis. A simple model to describe the relationship between dissociation and association reactions is proposed. (c) 2007 American Institute of Physics.

A multi-proxy palaeoenvironmental investigation of the findspot of an Iron Age bog body from Oldcroghan, Co. Offaly, Ireland

In 2003, the remains of an Early Iron Age bog body, known as ‘Oldcroghan Man’, were recovered during the cutting of a drainage ditch in a bog in the Irish Midlands. Only some fingernails and a withe fragment remained undisturbed in situ in the drain face, providing the sole evidence for the original position of the body. A detailed reconstruction of the depositional context of the body has been undertaken through multi-proxy analyses of a peat monolith collected at the findspot. The palynological record shows that the surrounding area was the focus of intensive human activity during the Later Bronze Age, but was largely abandoned during the Bronze Age–Iron transition in the mid-first millennium BC. In the mid-4th century BC, a bog pool developed at the site, evidenced in the stratigraphic, plant macrofossil, testate amoebae and coleopteran records. Plant macrofossil and pollen analysis of peat samples associated with the fingernails suggests that the body was deposited in this pool most likely during the 3rd century BC. The absence of carrion beetle fauna points to complete submergence of the body within the pool. Deposition occurred shortly before or around the time that the surrounding area again became the focus of woodland clearance, as seen in the extended pollen record from the peat monolith. This period corresponds to the Early Iron Age in Ireland, during which renewed cultural connections with Britain and continental Europe can be seen in the archaeological record and widespread forest clearance is recorded in pollen records from across Ireland. The palaeoenvironmental results indicate, therefore, that the demise of Oldcroghan Man took place at a pivotal time of socio-economic and perhaps political change.

Electron impact excitation of S-like iron

Energy levels and radiative rates for transitions among the lowest 48 fine-structure levels belonging to the (1s(2) 2s(2) 2p (6)) 3s (2)3p (4) , 3s3p(5), 3s (2)3p (3) 3d and 3p(6) configurations of Fe xi have been calculated using the fully relativistic grasp code. Additionally, collision strengths for transitions among these levels have also been computed using the Dirac Atomic R-matrix Code (darc) of Norrington & Grant. Radiative rates and oscillator strengths are tabulated for all allowed transitions among the 48 fine-structure levels, while collision strengths are reported at three energies above thresholds, i.e. 8, 16 and 24 Ryd for a few representative transitions. Furthermore, excitation rates have been calculated in a wide electron temperature range below 5 x 10(6) K, and the contribution of resonances has been included in the threshold regions. Comparisons are made with the earlier available theoretical and experimental rates, and it is concluded that the experimental rates are overestimated by up to a factor of 2.

The 1996 ‘Muslim holiday’ affair. Religious competition and state mediation in contemporary Mozambique

Political commentators often cast religious con? ict as the result of the numerical growth and political rise of a single faith. When Islam is involved, arguments about religious fundamentalism are quick to surface and often stand as an explanation in their own right. Yet, as useful as this type of explanation may be, it usually fails to address properly, if at all, two sets of important issues. It avoids, Ž rst, the question of the rise of other religions and their contribution to tensions and con? icts. Second, it reduces the role of the State to a reactive one. The State becomes an object of contest or conquest, or it is simply ignored. Adopting a different approach, this article investigates a controversy that took place in Mozambique in 1996 around the ‘ofŽ cialisation’ of two Islamic holidays. It looks at the role played by religious competition and state mediation. The article shows that the State’s abandonment of religious regulation – the establishment of a free ‘religious market’ – fostered religious competition that created tensions between faiths. It suggests that strife ensued because deregulation was almost absolute: the State did not take a clear stand in religious matters and faith organisations started to believe that the State was becoming, or could become, confessional. The conclusion discusses theoretical implications for the understanding of religious strife as well as Church and State relations. It also draws some implications for the case of Mozambique more speciŽ cally, implications which should have relevance for countries such as Malawi, Zambia and Zimbabwe where problems of a similar nature have arisen.

Influence of maternal diabetes mellitus on fetal iron status

OBJECTIVE: To determine the effects of maternal diabetes on fetal iron status using serum transferrin receptors (STfR) and their ratio to ferritin (TfR-F index) in cord blood. METHODS: Iron, ferritin, erythropoietin, STfR and haemoglobin concentration were measured and TfR-F index calculated in 97 maternal/cord blood pairs. Forty-nine women had type 1 diabetes (diagnosed before pregnancy) and these were compared with forty-eight non- diabetic controls. The women with type 1 diabetes were recruited consecutively from attendance at the joint antenatal endocrine clinic while the control group of women was recruited from consecutive attendance at the remaining antenatal clinics. RESULTS: The infants of the diabetic women had significantly lower levels of ferritin (47 vs 169 mug/l; p

Tuberculosis among Iron Age individuals from Tyva, South Siberia: palaeopathological and biomolecular findings

The study focuses on the evidence for tuberculosis apparent in an Iron Age population recovered from the cemetery of Aymyrlyg, Tyva (Tuva), South Siberia. A recent wholly molecular study of five of the cases confirmed the presence of Mycobacterium tuberculosis (MTB) complex DNA in four of the individuals. In all cases the disease was caused by strains of Mycobacterium bovis rather than Mycobacterium tuberculosis and represents the first positive identification of the bovine form of the disease in archaeological human remains. Details of the palaeopathological characteristics of the cases are provided in the current paper, while the molecular observations are extended to include a quantitative evaluation of the surviving mycobacterial DNA using real-time PCR. The observation that bovine tuberculosis was the pathogen responsible is discussed in terms of current understanding of the evolution of the MTB complex as well as the implications for future ancient DNA studies in this area.

Ten Year Performance Evaluation of a Field-Scale Zero-Valent Iron Permeable Reactive Barrier Installed to Remediate Trichloroethene Contaminated Groundwater

The Monkstown Fe0 PRB, Europe’s oldest commercially installed PRB, had been treating trichloroethene (TCE) contaminated groundwater for about 10 years on the Nortel Network site in Northern Ireland when cores were collected in December, 2006. Groundwater data from 2001-2006 indicated that TCE is being remediated to below detection limits as the contaminated groundwater flows through the PRB, Ca and Fe carbonates, crystalline and amorphous FeS, and Fe (oxy)hydroxides precipitates are present in the Fe0 filing material within the PRB. A greater variety of minerals are associated with a 1 cm thick slightly cemented crust at the entrance of the Fe0 section of the reactive vessel and the discontinuous cemented Fe0 material directly below it. Also, a greater presence of microbial communities occurred in the upper portion of the PRB compared to the lower section which might be due to less favourable conditions (i.e. high pH, low oxygen) for microbial growth in the lower section of the PRB. Visual estimation suggests that the Fe0 filings in the effluent section of the PRB have life-span of 10+ years compared to the Fe0 filings in the thin influent section of the PRB which may have a life span of only ~2-5 more years. Multi-tracer tests indicated that preferential pathways have formed in this PRB over the 10 years of operation.

Deep weathering of calcareous sedimentary rock and the redistribution of iron and manganese in soil and saprolite

Iron and Mn redistribute in soil and saprolite during weathering. The geological weathering fronts ofcalcareous sedimentary rock were investigated by examining the bulk density, porosity, and distribution ofCa, Fe, and Mn. Core samples were taken ofsoil, saprolite, and bedrock material from both summit (HHMS-4B) and sideslope (HHMS-5A) positions on an interbedded Nolichucky shale and Maryville limestone landform in Solid Waste Storage Area 6 (SWSA-6). This is a low-level radioactive solids waste disposal site on the Dept. ofEnergy (DOE) Oak Ridge Reservation in Roane County Tennessee. This work was initiated because data about the properties of highly weathered sedimentary rock on this site were limited. The core samples were analyzed for pH, calcium carbonate equivalence (CCE), hydroxylamine-extractable (HA) Mn, and dithionite-citrate (CBD)-extractable Fe and Mn. Low pH values occurred from the soil surface down to the depth of the oxidized and leached saprolite in both cores. The CCE and HA-extractable Mn results were also influenced by the weathering that has occurred in these zones. Extractable Mn oxide was higher at a lower depth in the oxidized and leached saprolite compared with the Fe oxide, which was higher in the overlying soil solum. Amounts of Mn oxides were higher in the sideslope core (HHMS-5A) than in the summit core (HHMS-4B). Iron was more abundant in the deeper weathered summit core, but the highest value, 39.4 g kg-1, was found at 1.8 to 2.4 m in the sideslope core. The zone encompassing the oxidized and partially leached saprolite down to the unoxidized and unleached bedrock had higher densities and larger quantities of CaCO3 than the soil solum and oxidized and leached saprolite. The overlying soil and oxidized and leached saprolite had lower pH and CCE values and were higher in Fe and Mn oxides than the oxidized and unleached saprolite. The distribution of Fe and Mn is important when evaluating soil and saprolite for hazardous waste disposal site assessment.

Performance evaluation of a zerovalent iron reactive barrier: Mineralogical characteristics

There is a limited amount of information about the effects of mineral precipitates and corrosion on the lifespan and long-term performance of in situ Fe° reactive barriers. The objectives of this paper are (1) to investigate mineral precipitates through an in situ permeable Fe° reactive barrier and (2) to examine the cementation and corrosion of Fe° filings in order to estimate the lifespan of this barrier. This field scale barrier (225' long x 2' wide x 31' deep) has been installed in order to remove uranium from contaminated groundwater at the Y-12 plant site, Oak Ridge, TN. According to XRD and SEM-EDX analysis of core samples recovered from the Fe° portion of the barrier, iron oxyhydroxides were found throughout, while aragonite, siderite, and FeS occurred predominantly in the shallow portion. Additionally, aragonite and FeS were present in up-gradient deeper zone where groundwater first enters the Fe° section of the barrier. After 15 months in the barrier, most of the Fe° filings in the core samples were loose, and a little corrosion of Fe° filings was observed in most of the barrier. However, larger amounts of corrosion (~10-150 µm thick corrosion rinds) occurred on cemented iron particles where groundwater first enters the barrier. Bicarbonate/ carbonate concentrations were high in this section of the barrier. Byproducts of this corrosion, iron oxyhydroxides, were the primary binding material in the cementation. Also, aragonite acted as a binding material to a lesser extent, while amorphous FeS occurred as coatings and infilings. Thin corrosion rinds (2-50 µm thick) were also found on the uncemented individual Fe° filings in the same area of the cementation. If corrosion continues, the estimated lifespan of Fe° filings in the more corroded sections is 5 to 10 years, while the Fe° filings in the rest of the barrier perhaps would last longer than 15 years. The mineral precipitates on the Fe° filing surfaces may hinder this corrosion but they may also decrease reactive surfaces. This research shows that precipitation will vary across a single reactive barrier and that greater corrosion and subsequent cementation of the filings may occur where groundwater first enters the Fe° section of the barrier.