Characterization,dissolution and solubility of the hydroxypyromorphite–hydroxyapatite solid solution [(Pb<Subscript>x</Subscript>Ca<Subscript>1−x</Subscript>)<Subscript>5</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>OH] at 25 °C and pH 2–9

Background

The interaction between Ca-HAP and Pb²⁺ solution can result in the formation of a hydroxyapatite–hydroxypyromorphite solid solution [(Pb_xCa_1?x)₅(PO₄)₃(OH)], which can greatly affect the transport and distribution of toxic Pb in water, rock and soil. Therefore, it’s necessary to know the physicochemical properties of (Pb_xCa_1?x)₅(PO₄)₃(OH), predominantly its thermodynamic solubility and stability in aqueous solution. Nevertheless, no experiment on the dissolution and related thermodynamic data has been reported.

Results

Dissolution of the hydroxypyromorphite–hydroxyapatite solid solution [(Pb_xCa_1?x)₅(PO₄)₃(OH)] in aqueous solution at 25 °C was experimentally studied. The aqueous concentrations were greatly affected by the Pb/(Pb + Ca) molar ratios (X_Pb) of the solids. For the solids with high X_Pb [(Pb_0.89Ca_0.11)₅(PO₄)₃OH], the aqueous Pb²⁺ concentrations increased rapidly with time and reached a peak value after 240–720 h dissolution, and then decreased gradually and reached a stable state after 5040 h dissolution. For the solids with low X_Pb (0.00–0.80), the aqueous Pb²⁺ concentrations increased quickly with time and reached a peak value after 1–12 h dissolution, and then decreased gradually and attained a stable state after 720–2160 h dissolution.

Conclusions

The dissolution process of the solids with high X_Pb (0.89–1.00) was different from that of the solids with low X_Pb (0.00–0.80). The average K _sp values were estimated to be 10^?80.77±0.20 (10^?80.57–10^?80.96) for hydroxypyromorphite [Pb₅(PO₄)₃OH] and 10^?58.38±0.07 (10^?58.31–10^?58.46) for calcium hydroxyapatite [Ca₅(PO₄)₃OH]. The Gibbs free energies of formation (ΔG _f ^o ) were determined to be ?3796.71 and ?6314.63 kJ/mol, respectively. The solubility decreased with the increasing Pb/(Pb + Ca) molar ratios (X_Pb) of (Pb_xCa_1?x)₅(PO₄)₃(OH). For the dissolution at 25 °C with an initial pH of 2.00, the experimental data plotted on the Lippmann diagram showed that the solid solution (Pb_xCa_1?x)₅(PO₄)₃(OH) dissolved stoichiometrically at the early stage of dissolution and moved gradually up to the Lippmann solutus curve and the saturation curve for Pb₅(PO₄)₃OH, and then the data points moved along the Lippmann solutus curve from right to left. The Pb-rich (Pb_xCa_1?x)₅(PO₄)₃(OH) was in equilibrium with the Ca-rich aqueous solution.

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Graphical abstractLippmann diagrams for dissolution of the hydroxypyromorphite–hydroxyapatite solid solution [(Pb_xCa_1?x)₅(PO₄)₃OH] at 25??C and an initial pH of 2.00.

     

Landslide detection and susceptibility mapping using LiDAR and an artificial neural network approach: a case study in the Cuyahoga Valley National Park,Ohio

The purpose of this study was to detect shallow landslides using hillshade maps derived from light detection and ranging (LiDAR)-based digital elevation model (DEM) derivatives. The landslide susceptibility mapping used an artificial neural network (ANN) approach and backpropagation method that was tested in the northern portion of the Cuyahoga Valley National Park (CVNP) located in northeast Ohio. The relationship between landslides and predictor attributes, which describe landform classes using slope, profile and plan curvatures, upslope drainage area, annual solar radiation, and wetness index, was extracted from LiDAR-based DEM using geographic information system (GIS). The approach presented in this paper required a training study area for the development of the susceptibility model and a validation study area to test the model. The results from the validation showed that within the very high susceptibility class, a total of 42.6 % of known landslides that were associated with 1.56 % of total area were correctly predicted. In contrast, the very low susceptibility class that represented 82.68 % of the total area was associated with 1.20 % of known landslides. The results suggest that the majority of the known landslides occur within a small portion of the study area, consistent with field investigation and other studies. Sample probabilistic maps of landslide susceptibility potential and other products from this approach are summarized and presented for visualization to help park officials in effective management and planning.     

Linear discriminant analysis to describe the relationship between rainfall and landslides in Bogotá, Colombia

Bogotá is located in the central Andean region of Colombia, which is frequently affected by landslide processes. These processes are mostly triggered during the rainy season in the city. This fact remarks the importance of determining what rain-derived parameters (e.g. intensity, antecedent rain, daily rain) are better related with the occurrence of landslides. For this purpose, the linear discriminant analysis (LDA), a technique derived from multivariate statistics, was used. The application of this type of analysis led to obtain simple mathematical functions that represent the probability of occurrence of landslides in Bogotá. The functions also allow to identify the most relevant variables derived from records of rainfall linked to the generation of landslides. A proof of concept using the proposed methodology was done using historic rainfall data from a 9-km² area of homogenous climatology and geomorphology in the south part of Bogotá. Landslides needed to be grouped for the LDA. Each one of these grouping categories represents landslides that occurred in similar geomorphologic conditions. Another set of events with no landslides was generated synthetically. Results of the proof of concept show that rainfall parameters such as normalized rainfall intensity I _MAP, normalized daily rainfall R _MAP and rainy-days normal RDN have the best statistical correlation with the landslides observed in the zone of analysis.     

Field investigation of deformation characteristics and stress mobilisation of a soil slope

Stress mobilisation and deformation of a slope are important for engineers to carry out reliable design of retaining systems. However, most case histories reported mainly on the response of pore water pressure (PWP), whereas knowledge about the stress deformation characteristics of slope is limited. In this study, a saprolitic soil slope was instrumented to monitor not only the responses of PWP but also horizontal stress and horizontal displacement. To assist in the interpretation of field data, a series of laboratory tests was conducted to characterise volume change behaviour of the soil taken from the site, under the effects of both net stress and suction. During a rainstorm event when positive PWP built up, a remarkably large displacement of 20 mm was recorded between 5.5- and 6-m depths, and the top 5 m of the slope exhibited translational downslope movement. This caused an increase in Bishop’s effective horizontal stress by 350 %, which reached a peak value close to 40 % of a Bishop’s effective passive stress. During the subsequent dry season when suction was recovered, an upslope rebound of 10 mm was recorded. Comparison of field and laboratory data reveals that the rebound was attributed to suction-induced soil shrinkage. This rebound led to a decrease in the Bishop’s effective horizontal stress previously built up during the storm event.     

Engineering geomorphological characterisation of the Vajont Slide,Italy, and a new interpretation of the chronology and evolution of the landslide

Although the 1963 Vajont Slide in Italy has been extensively studied for over 50 years, its regional geological and geomorphological context has been neglected. In this paper, we use field observations and remote sensing data to elucidate the interaction between endogenic and exogenic processes that brought the north slope of Monte Toc to failure. We present the first detailed pre- and post-failure engineering geomorphology maps of the slide area. The maps delineate two main landslide blocks, several sub-blocks, compressional and extensional zones, and secondary failures in the deposit. The maps provide new insights into the kinematics, dynamics and evolution of the slide. Finally, we discuss the origin of Vajont Gorge and a prehistoric failure that occurred at the same location as the 1963 slide. We propose, as part of a newly developed multi-stage landscape evolution sequence, that the prehistoric failure was a deep-seated gravitational slope deformation (sackung) that initiated during deglaciation and continued to slowly move until the catastrophic failure in 1963. We argue that the gorge was created by these deep-seated slow movements.     

The August 27, 2014, rock avalanche and related impulse water waves in Fuquan,Guizhou, China

At about 8:30 p.m. on 27 August 2014, a catastrophic rock avalanche suddenly occurred in Fuquan, Yunnan, southwestern China. This landslide and related impulse water waves destroyed two villages and killed 23 persons. The impulse waves occurred after initiation of the landslide, caused by the main part of the slide mass rapidly plunging into a water-filled quarry below the source area. The wave, comprising muddy water and rock debris, impacted the opposite slope of the quarry on the western side of the runout path and washed away three homes in Xinwan village. Part of the displaced material traveled a horizontal distance of about 40 m from its source and destroyed the village of Xiaoba. To provide information for potential landslide hazard zonation in this area, a combined landslide–wave simulation was undertaken. A dynamic landslide analysis (DAN-W) model is used to simulate the landslide propagation before entering the quarry, while Fluent (Ansys Inc., USA) is used to simulate the impulse wave generation and propagation. Output data from the DAN-W simulation are used as input parameters for wave modeling, and there is good agreement between the observed and simulated results of the landslide propagation. Notably, the locations affected by recordable waves according to the simulation correspond to those recorded by field investigation.     

Use of targets to track 3D displacements in highly vegetated areas affected by landslides

Monitoring landslides with terrestrial laser scanning (TLS) is currently a well-known technique. One problem often encountered is the vegetation that produces shadow areas on the scans. Indeed, the points behind a given obstacle are hidden and thus occluded on the point cloud. Thereby, locations monitored with terrestrial laser scanner are mostly rock instabilities and few vegetated landslides, being difficult or even impossible to survey vegetated slopes using this method with its classical non-full wave form. The Peney landslide (Geneva, Switzerland) is partially vegetated by bushes and trees, and in order to monitor its displacements during the drawdown of the Verbois reservoir located at its base, an alternative solution has been found. We combined LiDAR technique with 14 targets made of polystyrene placed at different locations inside and outside the landslide area. The obtained displacements were compared with classical measurement methods (total station and extensometer), showing good resemblance of results, indicating that the use of targets in highly vegetated areas could be an efficient alternative for mass movements monitoring.     

Calculation method for thickness of discontinuous boundary layer of engineering pavement

The boundary layer is a buffer layer of water and heat exchange between the atmosphere and permafrost.Based on the atmospheric boundary layer and heat transfer theory,we established a method for determining the boundary layer thickness of engineering pavement(asphalt and sand pavement)in permafrost region.The boundary layer can be divided into the Boundary Layer Above Surface(BLAS)and the Boundary Layer Below Surface(BLBS).From in-situ monitoring data,the thickness of BLAS was determined through the laminar thickness,and the thickness of BLBS was determined through ground temperature,the heat conduction function,and the mean attenuation function(α).For asphalt pavement,the BLAS thickness varied between 2.90 and 4.31 mm and that of BLBS varied between 28.00 and 45.38 cm.For sand pavement,the BLAS thickness varied between 2.55 and 3.29 mm and that of BLBS varied between 15.00 and 46.44 cm.The thickness varied with freezing and thawing processes.The boundary layer calculation method described in this paper can provide a relatively stable boundary for temperature field analysis.     

Spatio-temporal evolution of urban innovation structure based on zip code geodatabase: An empirical study from Shanghai and Beijing

In today’s world, the innovation of science and technology has become the key support for improving comprehensive national strength and changing the mode of social production and lifestyle. The country that possesses world-class scientific and technological innovation cities maximizes the attraction of global innovation factors and wins a strategic initiative in international competition. Based on the urban zip code geodatabase, an evaluation system of urban innovation with the perspective of innovation outputs, and the spatial evolutionary mode, concerning the structure of innovation space of Shanghai and Beijing from 1991 to 2014, was developed. The results of the research indicated that the zip code geodatabase provided a new perspective for studying the evolving spatial structure of urban innovation. The resulting evaluation of the spatial structure of urban innovation using the urban zip code geodatabase established by connecting random edge points, was relatively effective. The study illustrates the value of this methodology. During the study period, the spatial structure of innovation of Shanghai and Beijing demonstrated many common features: with the increase in urban space units participating in innovation year by year, the overall gap of regional innovation outputs has narrowed, and the trend towards spatial agglomeration has strengthened. The evolving spatial structure of innovation of Shanghai and Beijing demonstrated differences between the common features during the 25 years as well: in the trend towards the suburbanization of innovation resources, the spatial structure of innovation of Shanghai evolved from a single-core to a multi-core structure. A radiation effect related to traffic arteries as spatial diffusion corridors was prominent. Accordingly, a spatial correlation effect of its innovation outputs also indicated a hollowness in the city center; the spatial structure of innovation of Beijing had a single-core oriented structure all the way. Together with the tendency for innovation resources to be agglomerated in the city center, the spatial correlation effect of innovation outputs reflected the characteristics of the evolutionary feature where “rural area encircles cities”. The innovation spatial structure of Shanghai and Beijing have intrinsic consistency with the spatial structure of their respective regions (Yangtze River Delta urban agglomeration and Beijing-Tianjin-Hebei metropolitan region), which suggested that the principle of proportional and disproportional distribution of a city-scale pattern of technological and innovational activities is closely related to its regional innovation pattern.