Long-term performance evaluation of zero-valent iron amended permeable reactive barriers for groundwater remediation – A mechanistic approach

Permeable reactive barriers (PRBs) are used for groundwater remediation at contaminated sites worldwide. This technology has been efficient at appropriate sites for treating organic and inorganic contaminants using zero-valent iron (ZVI) as a reductant and as a reactive material. Continued development of the technology over the years suggests that a robust understanding of PRB performance and the mechanisms involved is still lacking. Conflicting information in the scientific literature downplays the critical role of ZVI corrosion in the remediation of various organic and inorganic pollutants. Additionally, there is a lack of information on how different mechanisms act in tandem to affect ZVI-groundwater systems through time. In this review paper, we describe the underlying mechanisms of PRB performance and remove isolated misconceptions. We discuss the primary mechanisms of ZVI transformation and aging in PRBs and the role of iron corrosion products. We review numerous sites to reinforce our understanding of the interactions between groundwater contaminants and ZVI and the authigenic minerals that form within PRBs. Our findings show that ZVI corrosion products and mineral precipitates play critical roles in the long-term performance of PRBs by influencing the reactivity of ZVI. Pore occlusion by mineral precipitates occurs at the influent side of PRBs and is enhanced by dissolved oxygen and groundwater rich in dissolved solids and high alkalinity, which negatively impacts hydraulic conductivity, allowing contaminants to potentially bypass the treatment zone. Further development of site characterization tools and models is needed to support effective PRB designs for groundwater remediation.     

沉积盆地流体—岩石相互作用研究的现状

沉积盆地流体－岩石相互作用研究主要是通过实验地球化学和岩石学，地球化学模拟方法开展的，综述了这一领域的研究现状，主要包括有机酸来源和分布及期 对矿物稳定性的影响，地层水成因与演化、烃类与岩石间的氧化还原反应、以及储层润湿性的变化等，并展望了其 发展趋势。     

Geodynamic modelling of the Century deposit,Mt Isa Province,Queensland

This paper is concerned with an example of quantitative modelling of orebody formation as a guide to reducing the risk for future mineral exploration. Specifically, the paper presents a detailed 3–D numerical model for the formation of the Century zinc deposit in northern Queensland. The model couples fluid flow with deformation, thermal transport and chemical reactions. The emphasis of the study is a systems approach where the holistic mineralising system is considered rather than concentrating solely on the mineral deposit. In so doing the complete plumbing system for mineralisation is considered with a view to specifying the critical conditions responsible for the ore deposit occurring where it does and having the size and metal grades that are observed. The numerical model is based on detailed geological, tectonic, isotopic and mineralogical data collected over the past 20 years. The conclusions are that the Century zinc deposit is located where it is because of the following factors: (i) a thermal anomaly is associated with the Termite Range Fault due to advection of heat from depth by fluid flow up the Termite Range Fault; (ii) bedding‐plane fissility in the shale rocks hosting the Century zinc deposit has controlled the wavelength and nature of D₁ folding in the vicinity of the deposit and has also controlled increases in permeability due to hydrofracture of the shales; such hydrofracture is also associated with the production of hydrocarbons as these shales passed through the ‘oil‐window’; (iii) Pb–Zn leached from crustal rocks in the stratigraphic column migrated up along faults normal to the Termite Range Fault driven by topographic relief associated with inversion at the end of the Isan Orogeny; these fluids mixed with H₂S derived at depth moving up the Termite Range Fault to mix with the crustal fluids to precipitate Pb–Zn in a plume downstream from the point of mixing. Critical factors to be used as exploration guides are high temperatures, carbonaceous fissile shales now folded into relatively tight D₁ folds, fault‐controlled plumbing systems that enable fluid mixing, depletion of metals upstream of the deposit and,in particular,a very wide Fe‐depletion halo upstream of the deposit.     

Methoxy formation in the reaction of CH3O2 radicals with NO

Formation of methoxy (CH₃O) radicals in the reaction (1) CH₃O₂+NOCH₃O+NO₂ at 298 K has been observed directly using time resolved LIF. The branching ratio % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaeqOXdyMaae% 4qaiaabIeadaWgaaWcbaGaae4maaqabaGccaqGpbGaaeiiaiaabIca% ieqacaWF9aGaa8hiaiaa-nbicaWFGaGaeuiLdqKaai4waiaaboeaca% qGibWaaSbaaSqaaiaabodaaeqaaOGaae4taiaac2facaWFVaGaeuiL% dqKaai4waiaaboeacaqGibWaaSbaaSqaaiaabodaaeqaaOGaae4tam% aaBaaaleaacaqGYaaabeaakiaac2facaqGPaaaaa!4E31!\[\phi {\rm{CH}}_{\rm{3}} {\rm{O (}} = -- \Delta [{\rm{CH}}_{\rm{3}} {\rm{O}}]/\Delta [{\rm{CH}}_{\rm{3}} {\rm{O}}_{\rm{2}} ]{\rm{)}}\] has been determined by quantitative cw-UV-laser absorption at 257 nm of CH₃O₂ and CH₃ONO, the product of the consecutive methoxy trapping reaction (2) % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaae4qaiaabI% eadaWgaaWcbaGaae4maaqabaGccaqGpbacbeGaa83kaiaa-bcaieaa% caGFobGaa43taiaa+bcacaGFOaGaa83kaiaa+1eacaGFPaGaa4hiai% abgkziUkaabccacaqGdbGaaeisamaaBaaaleaacaqGZaaabeaakiaa% b+eacaqGGaGaaeOtaiaab+eacaqGGaGaa4hkaiaa-TcacaGFnbGaa4% xkaiaa+5cacaGFGaGaa4hiaiabeA8aMnaaBaaajqwaacqaaiaaboea% caqGibWaaSbaaKazcaiabaGaae4maaqabaqcKfaGaiaab+eaaSqaba% aaaa!55AC!\[{\rm{CH}}_{\rm{3}} {\rm{O}} + NO ( + M) \to {\rm{ CH}}_{\rm{3}} {\rm{O NO }}( + M). \phi _{{\rm{CH}}_{\rm{3}} {\rm{O}}} \] is found to be (1.0±0.2). The rate constant k ₁ is (7±2) 10^-12 cm³/molecule · s in good agreement with previous results.     

A Eulerian air pollution model for Europe with nonlinear chemistry

A long-range transport model with nonlinear chemical reactions is described. The model contains 35 pollutants and 70 chemical reactions. This is a Eulerian model defined on a space domain containing the whole of Europe. The spherical space domain (corresponding to the Earth's surface covered by the model) is mapped into a square plane domain and discretized by using a 32×32 grid. The grid increments are equidistant (both along the Ox axis and along the Oy axis). The choice of values of the physical parameters involved in the model and the numerical treatment of the model are shortly discussed. The model is tested with meteorological data for 1985 and 1989. The numerical results are compared with measurements at stations located in different European countries. Extensive comparisons of ozone concentrations for July 1985 with measurements taken at 24 European stations are also carried out. Results concerning three episodes in July 1985 as well as results obtained in the study of the sensitivity of the ozone concentrations to variations of NO _x and/or anthropogenic VOC emissions are presented. The advantages and the limitations of such a model are discussed. The model is continuously improved by adding new modules to it. The plans for improvements in the near future are outlined.     

I_a型超新星爆发理论(Ⅱ):理论研究中的重要疑难问题

介绍与评述了I_a型超新星理论研究中最为突出的8个尚未解决的重要疑难问题,并简单介绍了国内围绕SNI_a开展的某些物理探讨研究．     

Heavy-element abundances in seven SC stars and several related stars

We employ spectra of resolution 20–35000 of seven SC stars, four S stars, two Ba stars and two K–M stars to derive abundances of a variety of elements from Sr to Eu relative to iron. Special attention is paid to Rb and Tc, and to the ratio of the heavy s-process species to the light s-process elements. Abundances are derived in LTE, both by using model atmospheres in which the carbon and oxygen abundances are nearly equal and by using curves of growth. Spectrum synthesis is used for critical lines such as the 5924-Å line of Tc and the 7800-Å line of Rb. For most of the heavy-element stars the enhancement of the s-process elements is about a factor of 10. The ratio of the heavy to light s-process species is not far from solar, except for RR Her for which the same ratio is +0.45 dex. For Tc the blending by other lines is severe. While we have probably detected the 5924-Å line, we can only present abundances in the less-than-or-equal-to category. For Rb, whose abundance is sensitive to the ⁸⁵Rb/⁸⁷Rb ratio and hence to the neutron density during s-process production, we find a considerable range of abundances, indicating a neutron density from 10⁶ to ≳10⁸ cm⁻³ for the SC stars. For the four S stars the range is from 10⁷ to ≳10⁸ cm⁻³. Recent calculations by Gallino et al. show that neutron densities near 10⁷ cm⁻³ favour the ¹³C source for neutrons, while densities greater than 10⁸ cm⁻³ may be associated with neutrons from the ²²Ne source.     

Measurements of Reaction Coefficients of NO2 and HONO on Aerosol Particles

The reaction coefficients of nitrogen dioxide and nitrous acid with monodisperse sodium chloride and ammonium sulphate aerosols have been measured in a flow reactor at atmospheric pressure. These experiments were performed at relative humidities above and below the deliquescence points of both aerosols (r.h. 50 and 85%) at 279 K. The results for NO₂ afford a reaction coefficient in the range (2.8–10) × 10^-4 and for HONO, (2.8–4.6) × 10^-3. For both species, there appears to be an enhancement of the reaction coefficient on sodium chloride aerosol at 50% r.h. The results are compared with reaction coefficients determined by other experimental methods. A good agreement is found for both gases between this method and the coated denuder method previously developed in our research laboratories (Msibi et al., 1993) and with the majority of other published data for NO₂. In the case of HONO, our estimate of reaction coefficient is smaller than, or at the lower limits of the ranges reported by other published studies.