Langmuir films of polycyclic molecules on mercury

Langmuir films (LFs) of biphenyl and anthracene derivatives on the surface of liquid mercury were studied by surface-specific X-ray and surface tension measurements. Phases of lying-down, side-lying and standing-up molecules were found, some of which exhibit long-range lateral order. The molecular symmetry and the position and nature of the side-, end-, and headgroups are shown to dominate the structural evolution of the LFs with surface coverage.     

Predictive modeling of mercury speciation in combustion flue gases using GMDH-based abductive networks

Modeling mercury speciation is an important requirement for estimating harmful emissions from coal-fired power plants and developing strategies to reduce them. First-principle models based on chemical, kinetic, and thermodynamic aspects exist, but these are complex and difficult to develop. The use of modern data-based machine learning techniques has been recently introduced, including neural networks. Here we propose an alternative approach using abductive networks based on the group method of data handling (GMDH) algorithm, with the advantages of simplified and more automated model synthesis, automatic selection of significant inputs, and more transparent input–output model relationships. Models were developed for predicting three types of mercury speciation (elemental, oxidized, and particulate) using a small dataset containing six inputs parameters on the composition of the coal used and boiler operating conditions. Prediction performance compares favourably with neural network models developed using the same dataset, with correlation coefficients as high as 0.97 for training data. Network committees (ensembles) are proposed as a means of improving prediction accuracy, and suggestions are made for future work to further improve performance.     

A source apportioned mercury mass balance across a coal-based petrochemical complex

Coal-fired power generation facilities are the largest single anthropogenic source of mercury to the atmosphere. Global mapping of anthropogenic emissions has previously estimated the mercury emission from stationary combustion from South Africa at being 82.6 tonnes per annum, but preliminary in-house calculations have placed this at a significantly lower amount. A petrochemical facility in South Africa, utilising a significant amount of coal in its gasification and steam generation processes, undertook a project to determine a mercury mass balance across the complex, and to apportion the Hg emissions from the facility.     

How Non-native Species in Lake Erie Influence Trophic Transfer of Mercury and Lead to Top Predators

Lake Erie's food web has been dramatically modified by exotic species. Both exotic dreissenid mussels and the round goby Neogobius melanastomus have shifted the food web from a pelagicbased to a benthic-based one, potentially creating a new pathway for contaminant transfer to top predators. Before the invasion of round gobies, few predators of dreissenids occurred in Lake Erie, allowing contaminants to be confined to these benthic organisms. The invasion of the round goby has produced a new pathway through which these contaminants can enter the food web. To characterize heavy-metal transfer through this new food web and to assess risk to humans, water, surficial sediment, dreissenid, round goby, and smallmouth bass Micropterus dolomieui samples were collected at three sites during summers, 2002 and 2003, and analyzed for total lead (Pb), total mercury (Hg), and methyl mercury (MeHg). In addition, we compared smallmouth bass Pb and Hg concentrations to those measured in 1993/1994, before round gobies were prevalent. Pb biodiminished and MeHg biomagnified through the food web to smallmouth bass; patterns were similar among our three sites. Total Pb concentrations in smallmouth bass were higher before the incorporation of round gobies into their diet. We attributed this decline to changes in food web structure, changes in contaminant burdens in prey, or declines in sediment Pb concentrations in Lake Erie. By comparison, Hg concentrations in smallmouth bass changed little, before and after the round goby invasion, possibly due to a shift in diet that increased growth. Despite a decline in sediment Hg concentrations in Lake Erie, smallmouth bass continued to accumulate Hg at historical rates possibly because of their high consumption rates of benthivorous round gobies. As smallmouth bass continue to consume round gobies during their lives, their Hg concentrations may well continue to increase, potentially increasing the risk of Hg contamination to humans.     

Laboratory study of air-water-coal combustion product (fly ash and FGD solid) mercury exchange

Recent laboratory research has indicated that coal fly ash derived from subbituminous and bituminous type coals is a sink for atmospheric mercury (Hg), however lignite-based ash was found to emit Hg to the air. Solids collected from systems with components that enhance Hg removal (i.e. activated carbon injection (ACI), flue gas desulfurization (FGD), and selective catalytic reduction (SCR) or selective non-catalytic reduction (SNCR)) may have higher Hg concentrations and therefore a higher potential for Hg release. For this study we investigated the potential for Hg release to the air and water from coal combustion products (CCPs) collected from coal-fired units with FGD equipment, SCR and SNCR equipment, and sorbent injection for Hg removal. In the laboratory study, most dry samples acted as sinks for atmospheric Hg in the dark at 25 °C. When exposed to light or increased temperature (45 °C), deposition of Hg to the fly ash substrates in most cases continued but decreased. Wet FGD samples emitted Hg. However, they became a sink for atmospheric Hg or exhibited low Hg emission rates when dried. Mercury flux in the dark at 25 °C was correlated with fly ash carbon content (LOI). Most liquid extracts derived using the synthetic precipitation leaching procedure (SPLP EPA method 1312) had very low Hg concentrations (<13 ng/l).     

On the relationship between pore structure and chloride diffusivity from accelerated chloride migration test in cement-based materials

In this study the electrochemical technique is applied to accelerate chloride ion migration in concrete to determine the chloride ions in anode cell, and the pore characteristic of the same mortars in concrete was obtained from the mercury intrusion porosimetry (MIP). The plain ordinary Portland cement and the constant aggregate with eight w/c ratios ranging from 0.3 to 0.65 were used. A good linear relationship between the steady-state migration coefficient and non-steady-state migration coefficient based on the same experimental setup and specimens was obtained. Both of the steady-state migration coefficient and non-steady-state migration coefficient were linearly related to the capillary pore volume and the critical pore diameter.     

Effect of porous structure and surface functionality on the mercury capacity of a fly ash carbon and its activated sample

The effect of porous structure and surface functionality on the mercury capacity of a fly ash carbon and its activated sample has been investigated. The samples were tested for mercury adsorption using a fixed‐bed with a simulated flue gas. The activated fly ash carbon sample has lower mercury capacity than its precursor fly ash carbon (0.23 vs. 1.85 mg/g), although its surface area is around 15 times larger, 863 vs. 53 m²/g. It was found that oxygen functionality and the presence of halogen species on the surface of fly ash carbons may promote mercury adsorption, while the surface area does not seem to have a significant effect on their mercury capacity.     

Damage evolution analysis in mortar, during compressive loading using acoustic emission and X-ray tomography: Effects of the sand/cement ratio

This paper explores the use of acoustic emission (AE) and X-ray tomography to identify the mechanisms of damage and the fracture process during compressive loading on concrete specimens. Three-dimensional (3D) X-ray tomography image analysis was used to observe defects of virgin mortar specimen under different compressive loads. Cumulative AE events were used to evaluate damage process in real time according to the sand/cement ratio. This work shows that AE and X-ray tomography are complementary nondestructive methods to measure, characterise and locate damage sites in mortar. The effect of the sand proportion on damage and fracture behaviour is studied, in relation with the microstructure of the material.     

A porosimetric study of calcium sulfoaluminate cement pastes cured at early ages

Calcium sulfoaluminate and Portland cement pastes, both prepared with a water/solid mass ratio equal to 0.5 and cured for time periods comprised between 2 h and 28 days, show completely different pore size distributions by mercury intrusion. Portland cement pastes aged at 12 h and 1 day exhibit a unimodal distribution of pore sizes related to a continuous network of capillary pores with a threshold pore radius decreasing from nearly 650 to 350 nm. After 7 and 28 days of curing, this parameter shifts to about 150 nm and a region having smaller pores appears (with a second threshold pore radius roughly comprised between 10 and 30 nm), made discontinuous by blockages of hydration products which occlude the interconnected pore system and isolate the interior space. For calcium sulfoaluminate cement pastes, a bimodal distribution is rapidly established, in which the regions with a lower porosity (threshold pore radii up to about 25 nm) are dominant, while the decrease of total porosity almost ceases at later ages. The porosimetric behaviour of calcium sulfoaluminate-based cement is related to its very fast hydration rate and to the lack of water needed to continue the hydration reactions.     

原子荧光光谱法测定水产品中汞的条件选择及应用

参照食品中总汞及有机汞测定标准，对采用原子荧光光谱法测定食品中总汞的几个主要测定参数进行探讨。测定结果表明，在一定含汞量的范围内，该方法灵敏稳定，各种干扰大大降低，检出限0．15μg／L，标准曲线最佳线性范围0μg/L-60μg／L；线性相关系数（r）0．9999，RSD4％。平均标准回收率97—109％。方法快速、准确，实用性强。