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.     

重点区域海域使用权属核查的实践和思考

国家海洋局近年来启动重点区域海域使用权属核查工作,浙江省平阳县是全国首批4个海域使用权属核查试点区域之一。文章就平阳县海域使用权属核查实践中遇到的关键问题进行思考和探讨,并提出解决措施和建议,为开展全国海域使用权属核查提供经验。     

硫酸镁对仿刺参幼参麻醉效果的研究

本研究以硫酸镁作为麻醉剂,比较了在不同水温条件下硫酸镁对仿刺参幼参的麻醉效果,分析了不同浓度硫酸镁对仿刺参幼参的麻醉效果。实验水温设置11℃、13℃、15℃、17℃、19℃和21℃六个温度梯度,实验用仿刺参幼参规格分为大规格(L)40.26±1.84g、中规格(M)21.83±1.72g、小规格(S)11.03±1.63g。实验结果显示:1.在硫酸镁麻醉剂浓度相同时,仿刺参规格越大麻醉所需时间越长,复苏时间却越短;随着麻醉剂浓度增加,对仿刺参幼参麻醉时间相应缩短,但复苏时间呈现逐渐延长。不同浓度硫酸镁麻醉剂对不同规格仿刺参的麻醉效果具有显著差异(P0.05)。2.在水温11℃~20℃范围内,随着水温的升高,对仿刺参幼参的麻醉时间从26.13±17.78min缩短到21.47±3.52min,但复苏时间从26.13±17.78min增加到71.05±12.32min,不同水温条件下硫酸镁对仿刺参幼参麻醉效果影响显著(P0.05)。研究表明,仿刺参体重在20g以下的适宜麻醉浓度为0.1~0.25mol·L-1,体重在20g以上的适宜麻醉浓度为0.25~0.35mol·L~(-1)。