Synthesis and Characterization of Poly(2‐hydroxyethylmethacrylate‐hydroxyapatite) a Novel Composite for the Removal of Lead(II) from Aqueous Solutions

In the present study, a novel adsorbent, poly (2‐hydroxyethylmethacrylate‐hydroxyapatite) [P(HEMA‐Hap)], was prepared and characterized. The synthesis was achieved by means of free‐radical polymerization and a number of structural characterization methods, including FT‐IR, XRD, TGA, SEM, BET‐porosity, and swelling tests. Pb²⁺ adsorption was performed using a series of pH, time, and temperature ranges. The reusability of the composite was also tested. The results obtained indicated that the novel adsorbent is able to bind Pb²⁺ ions with strong chemical affinity. The adsorption results were fitted to the classic Langmuir, Freundlich, and Dubinin–Radushkevich (D–R) sorption models. Thermodynamic parameters obtained demonstrated that the sorption process was spontaneous (ΔG < 0), endothermic (ΔH > 0), as expected. The process was also consistent with the pseudo‐second‐order model, and chemical adsorption was determined to be the rate‐controlling step. It was also shown that the composite could be used for five consecutive adsorption processes.     

A Study: Removal of Cu(II), Cd(II), and Pb(II) Ions from Real Industrial Water and Contaminated Water Using Activated Sludge Biomass

This study aims to remove of Cu²⁺, Cd²⁺, and Pb²⁺ ions from solution and to investigate the adsorption isotherms, adsorption kinetics, and ion‐exchange affinities of these metals using waste activated sludge (AS) biomass. The adsorptions of the metals on biomass were optimal at an acidic pH value of 6.0 based on its monolayer capacities. Maximum monolayer capacities of AS biomass (q_max) were calculated as 0.478, 0.358, and 0.280 mmol g^?1 for Cu²⁺, Cd²⁺, and Pb²⁺, respectively, and the adsorption equilibrium time was found as 60 min for each metal. The adsorbed amount of metal rose with increasing of initial metal ion concentration. The equilibrium adsorption capacity of AS for initial 0.25 mmol L^?1 metal concentration was determined as 0.200, 0.167, and 0.155 mmol g^?1 for Cu²⁺, Cd²⁺, and Pb²⁺ ions, respectively. These relevant values were determined as 0.420, 0.305, and 0.282 mmol g^?1 for Cu²⁺, Cd²⁺, and Pb²⁺ ions, respectively, when initial metal concentration was 0.50 mmol L^?1. In the multi‐metal sorption system, the adsorption capacity of AS biomass was observed in the order of Cu²⁺ > Cd²⁺ > Pb²⁺. In the presence of 100 mmol L^?1 H⁺ ion, the order of ion‐exchange affinity with H⁺ was found as Cu²⁺ > Cd²⁺ > Pb²⁺. The adsorption kinetics were also found to be well described by the pseudo‐second‐order and intraparticle diffusion models. Two different rate constants were obtained as k_i1 and k_i2 and k_i1 (first stage) was found to be higher than k_i2 (second stage).     

Coprecipitation with Cu(II)‐4‐(2‐Pyridylazo)‐resorcinol for Separation and Preconcentration of Fe(III) and Ni(II) in Water and Food Samples

The coprecipitation method is widely used for the preconcentration of trace metal ions prior to their determination by flame atomic absorption spectrometry (FAAS). A simple and sensitive method based on coprecipitation of Fe(III) and Ni(II) ions with Cu(II)‐4‐(2‐pyridylazo)‐resorcinol was developed. The analytical parameters including pH, amount of copper (II), amount of reagent, sample volume, etc., were examined. It was found that the metal ions studied were quantitatively coprecipitated in the pH range of 5.0–6.5. The detection limits (DL) (n = 10, 3s/b) were found to be 0.68 µg L^?1 for Fe(III) and 0.43 µg L^?1 for Ni(II) and the relative standard deviations (RSD) were ≤4.0%. The proposed method was validated by the analysis of three certified reference materials (TMDA 54.4 fortified lake water, SRM 1568a rice flour, and GBW07605 tea) and recovery tests. The method was successfully applied to sea water, lake water, and various food samples.     

One‐Pot Synthesis of Xanthate‐Functionalized Cellulose for the Detection of Micromolar Copper(II) and Nickel(II) Ions

A one‐pot synthesis and application of cellulose‐based sensors to efficiently detect various toxic metal ions in aqueous solutions in micromolar quantities is reported. Cellulose microfibers have been functionalized with carbon disulfide in alkaline solution to form cellulose xanthate. The material detects several toxic metal ions such as copper, nickel, or cobalt ions through color change detectable by the naked eye. The optical sensor can be used as an ideal flash test for assessing the quality of drinking water.     

Preparation,Characterization and Adsorption Mechanism of Cu(II) onto Protonated Rubber Leaf Powder

The adsorption of Cu(II) onto HCl treated rubber leaf powder (HHBL) was investigated in batch and column studies. The adsorbent was characterized by spectroscopic and quantitative analyses in order to understand the mechanism of copper adsorption. HHBL is mesoporous in nature as indicated by Bruneuer, Emmett and Teller (BET) analysis, and has various kinds of functional groups such as Si‐OH, ROH, RCOOH, RCOO^–, RNH₂, C‐O‐C and aromatic rings as detected by Fourier transform infrared (FTIR) spectroscopy. Copper adsorption was confirmed by scanning electron microscopy (SEM) and energy dispersive X‐ray spectroscopy (EDS). The equilibrium process was described well by the Langmuir isotherm model, and a maximum adsorption capacity of 8.39 mg/g was recorded for the smallest adsorbent size (<180 μm). The two main adsorption mechanisms involved were ion exchange and complexation. The fixed bed column study demonstrated satisfactory applicability of HHBL in removing Cu(II) from aqueous solutions.     

Spatiotemporal analysis of climate variability (1971–2010) in spring and summer on the Loess Plateau,China

By using the Variable Infiltration Capacity model with Palmer Drought Severity Index (VIC‐PDSI) model and Standardized Precipitation Index (SPI), spatiotemporal trends of climate variation during the main growing seasons for plants of Loess Plateau between 1971 and 2010 were detected and characterized. The VIC‐PDSI model is established by combining the VIC model with PDSI. The simulation results and the grids system of VIC were applied to substitute for the two‐layer bucket‐type model to do the hydrological accounting, which could improve the physical mechanism of PDSI and expand its application range. Our results suggest that the climate of the study area has experienced a drying and warming trend during the past four decades. Apart from some individual years and regions, there was a perpetuation of water deficit over the Plateau both in spring and summer. The drought frequency increased from southeast to northwest in spring, while the drought frequency decreased from southeast to northwest in summer. The climate in the southern part of the Loess Plateau, accounting for 23.3% of the study region, showed a significant drying and warming trend in spring over the past four decades. The climate variability detected by VIC‐PDSI model shows good agreement with that monitored by SPI. Since a large part of the study region frequently suffered from water shortage during the main growing seasons for plants, people living in such drought‐prone areas should take measures to prevent the negative effects on agricultural production, reforestation, and regional food security caused by drought. Copyright © 2013 John Wiley & Sons, Ltd.     

Sensitive Ion‐Flotation Separation of Ag(I) Traces Using 2‐(2‐Methoxyphenyl)benzimidazole before Flame Atomic Absorption Spectrometric Determination in Water

A sensitive, reliable, and environmentally friendly method for simple separation and preconcentration of Ag(I) traces in aqueous samples is presented prior to their flame atomic absorption spectrometric determinations. At pH 7.0, Ag(I) was separated with 2‐(2‐methoxyphenyl)benzimidazole (MPBI) as a new complexing agent and floated after adding sodium dodecyl sulfate (SDS) as a foaming reagent. The floated layer was then dissolved in proper amount of concentrated nitric acid in methanol and introduced to the flame atomic absorption spectrometer (FAAS). The effects of pH, concentration of MPBI, type and amount of surfactant as the floating agent, type and amount of eluting agent, and influence of foreign ions on the recovery of the analyte ion were investigated. Also, using a nonlinear curve fitting method, the formation constant of 1.62 × 10⁶ was obtained for Ag(I)–MPBI complex. The analytical curve was linear in the range of 1.8 × 10^?7–1.7 × 10^?6 mol/L for determination of Ag(I). The relative standard deviation (RSD; N = 10) corresponding to 0.7 × 10^?6 mol/L of Ag(I), the limit of detection (10 blanks), and the enrichment factor were obtained as 1.7%, 2.9 × 10^?8 mol/L, and 43.0, respectively. The proposed procedure was then applied successfully for determination of silver ions in different water samples.     

Spatial and temporal variability of 0‐ to 5‐m soil–water storage at the watershed scale

Dynamic relationships among rainfall patterns, soil water distribution, and plant growth are crucial for sustainable conservation of soil and water resources in water‐limited ecosystems. Spatial and temporal variation in deep soil water content at a watershed scale have not yet been characterized adequately due to the lack of deep soil water data. Deep soil–water storage (SWS) up to a depth of 5 m (n = 73) was measured at 19 sampling occasions at the LaoYeManQu watershed on the Chinese Loess Plateau (CLP). At a depth of 0–1.5 m, the annual mean SWS was highly correlated with rain intensity, and the correlation decreased with depth, but within the layers at 1.5–5.0 m, the changes in SWS indicated a lag between precipitation and the replenishment of soil water. Geostatistical parameters of SWS were also highly dependent on depth, and the mean SWS presented similar spatial structures in two adjacent layers. Temporal stability of SWS as indicated by mean relative difference, standard deviation of the relative difference (SDRD), and mean absolute bias error (MABE) was significantly weaker at the shallow than at deeper layers. Soil separates and organic carbon content controlled the spatial pattern of SWS at the watershed scale. One representative location (Site 57) was identified to estimate the mean SWS in the 1‐ to 5‐m layer of the watershed. Semivariograms of the SDRD and MABE were best fitted by an isotropic spherical model, and their spatial distributions were depth‐dependent. Both temporal stability and spatial variability of SWS increased over depth. This study is helpful for deep SWS estimation and sustainable management of soil and water on the CLP, and for other similar regions around the world.     

Spatial and temporal variability of Canadian seasonal precipitation (1900–2000)

Wavelet and cross-wavelet analysis are used to identify and describe spatial and temporal variability in Canadian seasonal precipitation, and to gain further insights into the dynamical relationship between the seasonal precipitation and the dominant modes of climate variability in the Northern Hemisphere. Results from applying continuous wavelet transform to seasonal precipitation series from 201 stations selected from Environment Canada Meteorological Network reveal striking climate-related features before and after the 1940s. The span of available observations, 1900–2000, allows for depicting variance and covariance for periods up to 12 years. Scale-averaged wavelet power spectra are used to simultaneously assess the temporal and spatial variability in each set of 201 seasonal precipitation time series. The most striking feature, in the 2–3-year period and in the 3–6-year period—the 6–12-year period is dominated by white noise and is not considered further—is a net distinction between the timing and intensity of the temporal variability in autumn, winter and spring–summer precipitation. It is found that the autumn season exhibits the most intense activity (or variance) in both the 2–3 year and the 3–6 year periods. The winter season corresponds to the least intense activity for the 2–3 year period, but it exhibits more activity than the spring–summer for the 3–6 year period.Cross-wavelet analysis is provided between the seasonal precipitation and four selected climatic indices: the Pacific North America (PNA), the North Atlantic Oscillation (NAO), the Northern Hemisphere Annular Mode (NAM) originally called the Arctic Oscillation, and the sea surface temperature series over the Niño-3 region (ENSO). The wavelet cross-spectra revealed coherent space–time variability of the climate–precipitation relationship throughout Canada. It is shown that strong climate/precipitation activity (or covariance) in the 2–6 year period starts after 1940 whatever the climatic index and the season. Prior to year 1940, only local and weaker 2–6 year activity is revealed in western Canada essentially in winter and autumn, but overall a non-significant precipitation/climate relationship is observed prior to 1940. Correlation analysis in the 2–6 year band between the seasonal precipitation and the selected climatic indices revealed strong positive correlations with the ENSO, the NAO, and the NAM in eastern and western Canada for the post-1940 period. For the period prior to 1940, the correlation tend be negative for all the indices whatever the region. A particular feature in the correlation analysis results is the consistently stronger and positive NAM–precipitation correlations in all the regions since 1940. The cross-wavelet spectra and the correlation analysis in the 2–6 year band suggest the presence of a change point around 1940 in Canadian seasonal precipitation—that is found to be more likely related to NAM dynamics.     

Adsorbed and Bound Residues in Fulvic Acid Fractions of a Contaminated Groundwater – Isolation:, Chromatographic and Spectroscopic Characterization

Humic substances (HS) were isolated from two contaminated groundwater samples (B22 and B53) from a site of a former gas facility. The isolation yielded almost only the fulvic acid fractions (FA). For characterization spectroscopic (UV, fluorescence) and chromatographic techniques (hydrophobic interaction chromatography – HIC as well as size-exclusion chromatography – SEC) were applied. The sample designated B22 FA was collected from the contamination plume whereas the sample B53 FA was collected downstream. Distinct differences were exhibited by these samples. The UV and fluorescence spectra as well as the HIC and SEC chromatograms of the B53 FA sample resemble those of the FA fraction obtained from natural water (groundwater, bog). The HIC and SEC chromatograms reveal the presence of organic compounds in B22 FA which can be derived from coal tar contaminants or their metabolites. Some of the compounds can be extracted from the FA fraction with non-polar organic solvents indicating adsorptive forces between the contaminants and the FA fraction.     

Base Treated Cogon Grass (Imperata cylindrica) as an Adsorbent for the Removal of Ni(II): Kinetic,Isothermal and Fixed‐bed Column Studies

The adsorption of Ni(II) from aqueous solutions using base treated cogon grass or Imperata cylindrica (NHIC) was performed under batch and column modes. Batch experiments were conducted to determine the factors affecting adsorption such as pH, adsorbent dosage, initial nickel concentration, contact time and temperature. The fixed‐bed column experiment was performed to determine the practical applicability of NHIC and to obtain the breakthrough curve. Adsorption was fast as equilibrium was achieved within 60 min, and was best described by the pseudo second order model. According to the Langmuir model, a maximum adsorption capacity of 6.96 mg/g was observed at pH 5 and at a temperature of 313 K. Thermodynamic parameters such as ΔG⁰, ΔH⁰ and ΔS⁰ were calculated, and indicated that adsorption was a spontaneous and endothermic process. The mechanistic pathway of Ni(II) uptake was examined by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and energy dispersive X‐ray (EDX) spectroscopy. The Thomas and Yoon‐Nelson models were used to analyze the fixed‐bed column data.     

Magnitude–frequency relationship for debris flows on the fan of the Chalance torrent,Valgaudemar (French Alps)

In 1996 a large debris flow occurred on the fan of the Chalance torrent system, a tributary of the Séveraisse river, French Alps. To investigate the magnitude and frequency of such debris flows on this fan, fieldwork was carried out in the summer of 1998. Detailed investigation revealed that several debris flows have occurred in the past 200 years. Lichenometry was used as a dating technique to obtain the frequency of these debris‐flow events. Also the volume of these flows was estimated. With these data a magnitude–frequency relationship was constructed. This relationship shows a maximum magnitude of at least 50 × 10³ m³. Based on data for the past c. 150 years, a debris flow of such a volume appears to have a recurrence interval of approximately 34 years. Copyright © 2002 John Wiley & Sons, Ltd.     

Coupled groundwater flow and heat transport simulation for estimating transient aquifer–stream exchange at the lowland River Spree (Germany)

Subsurface flow and heat transport near Freienbrink, NE Germany, was simulated in order to study groundwater–surface water exchange between a floodplains aquifer and a section of the lowland River Spree and an adjacent oxbow. Groundwater exfiltration was the dominant process, and only fast surface water level rises resulted in temporary infiltration into the aquifer. The main groundwater flow paths are identified based on a 3D groundwater flow model. To estimate mass fluxes across the aquifer–surface water interfaces, a 2D flow and heat transport modelling approach along a transect of 12 piezometers was performed. Results of steady‐state and transient water level simulations show an overall high accuracy with a Spearman coefficient ρ = 0.9996 and root mean square error (RMSE) = 0.008 m. Based on small groundwater flow velocities of about 10^?7 to 10^?6 ms^?1, mean groundwater exfiltration rates of 233 l m^?2 d^?1 are calculated. Short periods of surface water infiltration into the aquifer do not exceed 10 days, and the infiltration rates are in the same range. The heat transport was modelled with slightly less accuracy (ρ = 0.8359 and RMSE = 0.34 °C). In contrast to the predominant groundwater exfiltration, surface water temperatures determine the calculated temperatures in the upper aquifer below both surface water bodies down to 10 m during the whole simulation period. These findings emphasize prevailing of heat conduction over advection in the upper aquifer zones, which seems to be typical for lowland streams with sandy aquifer materials and low hydraulic gradients. Moreover, this study shows the potential of coupled numerical flow and heat transport modelling to understand groundwater–surface water exchange processes in detail. Copyright © 2013 John Wiley & Sons, Ltd.     

Modelling and experimental study of coupled exchange of p,p′‐DDE and colloids in a flume simulated stream–streambed system

Stream–subsurface exchange plays a significant role in the fate and transport of contaminants in streams. It has been modelled explicitly by considering fundamental processes such as hydraulic exchange, colloid filtration, and contaminant interactions with streambed sediments and colloids. The models have been successfully applied to simulate the transport of inorganic metals and nutrients. In this study, laboratory experiments were conducted in a recirculating flume to investigate the exchange of a hydrophobic organic contaminant, p,p′‐dichloro‐diphenyl‐dichloroethane (DDE), between a stream and a quartz sand bed. A previously developed process‐based multiphase exchange model was modified by accounting for the p,p′‐DDE kinetic adsorption to and desorption from the bed sediments/colloids and was applied to interpret the experimental results. Model input parameters were obtained by conducting independent small‐scale batch experiments. Results indicate that the immobilization of p,p′‐DDE in the quartz sand bed can occur under representative natural stream conditions. The observed p,p′‐DDE exchange was successfully simulated by the process‐based model. The model sensitivity analysis results show that the exchange of p,p′‐DDE can be sensitive to either the sediment sorption/desorption parameters or colloidal parameters depending on the experimental conditions tested. For the experimental conditions employed here, the effect of colloids on contaminant transport is expected to be minimal, and the stream–subsurface exchange of p,p′‐DDE is dominated by the interaction of p,p′‐DDE with bed sediment. The work presented here contributes to a better mechanistic understanding of the complex transport process that hydrophobic organic contaminants undergo in natural streams and to the development of reliable, predictive models for the assessment of impacted streams. Copyright © 2015 John Wiley & Sons, Ltd.     

Assessing the spatial and temporal variation of the rainwater harvesting potential (1971–2010) on the Chinese Loess Plateau using the VIC model

Rainwater harvesting could increase the resilience of ecosystems on the Loess Plateau and thus ensure the sustainability of livelihoods that depend on them. As such, it is a key component of strategies for adapting to global climate change. In this study, we used a new method to quantify the rainwater harvesting potential (RWHP) across the whole Loess Plateau and to characterize its spatial and temporal variation over the last four decades on the basis of the variable infiltration capacity model. It was found that that the mean RWHP of the study region was 731.10 × 10⁸ m³, and the average water layer thickness was 114.34 mm. There is considerable scope for rainwater harvesting across the Loess Plateau as a whole, to the extent that it could potentially provide enough water to implement the ‘Grain for Green’ Project. The annual average RWHP decreased slightly from 1971 to 2010, and Hurst exponent analysis indicated that this trend will exhibit long‐term persistence. The annual RWHP was highest in the southeast of the Loess Plateau and lowest in the northwest. Areas with high RWHP values tended to be clustered around the middle reach of the Yellow River. For most areas, there was no significant change between 1971 and 2010. Those areas for which there was a significant decrease in RWHP were primarily located around the upper–middle reaches of the Weihe River, the upper reach of Jinghe River, the eastern Guanzhong Plain, the Qinhe River watershed and the area around Dongsheng. Quantitative assessments of RWHP are likely to be useful for guiding the development and use of innovative rainwater harvesting technologies around the world and could help to relieve the problems caused by water shortages on the Loess Plateau while simultaneously eliminate the major cause of soil erosion. Copyright © 2012 John Wiley & Sons, Ltd.     

Wide‐area estimates of evapotranspiration by red gum (Eucalyptus camaldulensis) and associated vegetation in the Murray–Darling River Basin,Australia

Floodplain red gum forests (Eucalyptus camaldulensis plus associated grasses, reeds and sedges) are sites of high biodiversity in otherwise arid regions of southeastern Australia. They depend on periodic floods from rivers, but dams and diversions have reduced flood frequencies and volumes, leading to deterioration of trees and associated biota. There is a need to determine their water requirements so environmental flows can be administered to maintain or restore the forests. Their water requirements include the frequency and extent of overbank flooding, which recharges the floodplain soils with water, as well as the actual amount of water consumed in evapotranspiration (ET). We estimated the flooding requirements and ET for a 38 134 ha area of red gum forest fed by the Murrumbidgee River in Yanga National Park, New South Wales. ET was estimated by three methods: sap flux sensors placed in individual trees; a remote sensing method based on the Enhanced Vegetation Index from MODIS satellite imagery and a water balance method based on differences between river flows into and out of the forest. The methods gave comparable estimates yet covered different spatial and temporal scales. We estimated flood frequency and volume requirements by comparing Normalized Difference Vegetation Index values from Landsat images with flood history from 1995 to 2014, which included both wet periods and dry periods. ET during wet years is about 50% of potential ET but is much less in dry years because of the trees' ability to control stomatal conductance. Based on our analyses plus other studies, red gum trees at this location require environmental flows of 2000 GL yr^?1 every other year, with peak flows of 20 000 ML d^?1, to produce flooding sufficient to keep them in good condition. However, only about 120–200 GL yr^?1 of river water is consumed in ET, with the remainder flowing out of the forest where it enters the Murray River system. Copyright © 2015 John Wiley & Sons, Ltd.