Adsorption of rare earth elements onto Carrizo sand: Experimental investigations and modeling with surface complexation

Rare earth element (REE) adsorption onto sand from a well characterized aquifer, the Carrizo Sand aquifer of Texas, has been investigated in the laboratory using a batch method. The aim was to improve our understanding of REE adsorption behavior across the REE series and to develop a surface complexation model for the REEs, which can be applied to real aquifer-groundwater systems. Our batch experiments show that REE adsorption onto Carrizo sand increases with increasing atomic number across the REE series. For each REE, adsorption increases with increasing pH, such that when pH >6.0, >98% of each REE is adsorbed onto Carrizo sand for all experimental solutions, including when actual groundwaters from the Carrizo Sand aquifer are used in the experiments. Rare earth element adsorption was not sensitive to ionic strength and total initial REE concentrations in our batch experiments. It is possible that the differences in experimental ionic strength conditions (i.e., 0.002-0.01 M NaCl) chosen were insufficient to affect REE adsorption behavior. However, cation competition (e.g., Ca, Mg, and Zn) did affect REE adsorption onto Carrizo sand, especially for light rare earth elements (LREEs) at low pH. Rare earth element adsorption onto Carrizo sand can be successfully modeled using a generalized two-layer surface complexation model. Our model calculations suggest that REE complexation with strong surface sites of Carrizo sand exceeds the stability of the aqueous complexes LnOH²⁺, LnSO₄⁺, and LnCO₃⁺, but not that of Ln(CO₃)₂^- or LnPO₄^o in Carrizo groundwaters. Thus, at low pH (<7.3), where major inorganic ligands did not effectively compete with surface sites for dissolved REEs, free metal ion (Ln³⁺) adsorption was sufficient to describe REE adsorption behavior. However, at higher pH (>7.3) where solution complexation of the dissolved REEs was strong, REEs were adsorbed not only as free metal ion (Ln³⁺) but also as aqueous complexes (e.g., as Ln(CO₃)₂^- in Carrizo groundwaters). Because heavy rare earth elements (HREEs) were preferentially adsorbed onto Carrizo sand compared to LREEs, original HREE-enriched fractionation patterns in Carrizo groundwaters from the recharge area flattened along the groundwater flow path in the Carrizo Sand aquifer due to adsorption of free- and solution-complexed REEs.     

Hydrologic response of engineered media in living roofs and bioretention to large rainfalls: experiments and modeling

The hydrologic response of engineered media plays an important role in determining a stormwater control measure's ability to reduce runoff volume, flow rate, timing, and pollutant loads. Five engineered media, typical of living roof and bioretention stormwater control measures, were investigated in laboratory column experiments for their hydrologic responses to steady, large inflow rates. The inflow, medium water content response, and outflow were all measured. The water flow mechanism (uniform flow vs. preferential flow) was investigated by analyzing medium water content response in terms of timing, magnitude, and sequence with depth. Modeling the hydrologic process was conducted in the HYDRUS‐1D software, applying the Richards equation for uniform flow modeling, and a mobile–immobile model for preferential flow modeling. Uniform flow existed in most cases, including all initially dry living roof media with bimodal pore size distributions and one bioretention medium with unimodal pore size distribution. The Richards equation can predict the outflow hydrograph reasonably well for uniform flow conditions when medium hydraulic properties are adequately represented by appropriate functions. Preferential flow was found in two media with bimodal pore size distributions. The occurrence of preferential flow is more likely due to the interaction between the bimodal pore structure and the initial water content rather than the large inflow rate.     

Lake sedimentary processes and vegetation changes over the last 45k cal a bp in the uplands of south-eastern Amazonia

This study addresses paleoclimate influences in a southern Amazonia ecotone based on multiproxy records from lakes of the Carajás region during the last 45k cal a bp. Wet and cool environmental conditions marked the initial deposition in shallow depressions with detrital sediments and high weathering rates until 40k cal a bp. Concomitantly, forest and C3 canga plants, along with cool-adapted taxa, developed; however, short drier episodes enabled expansion of C4 plants and diagenetic formation of siderite. A massive event of siderite formation occurred approximately 30k cal a bp under strong drier conditions. Afterwards, wet and cool environmental conditions returned and persisted until the Last Glacial Maximum (LGM). The LGM was marked by lake-level lowstands and subaerial exposure. The transition from the LGM to the Holocene is marked by the onset of oscillations in temperature and humidity, with an expansion of forest and canga plants. Cool taxa were present for the last time in the Carajás region ~ 9.5–9k cal a bp. After 10k cal a bp , shallow lakes became upland swamps due to natural infilling processes, but the current vegetation types and structures of the plateaus were acquired only after 3k cal a bp under wetter climatic conditions.     

Climate change and future flows of Rocky Mountain rivers: converging forecasts from empirical trend projection and down‐scaled global circulation modelling

To predict future river flows, empirical trend projection (ETP) analyses and extends historic trends, while hydroclimatic modelling (HCM) incorporates regional downscaling from global circulation model (GCM) outputs. We applied both approaches to the extensively allocated Oldman River Basin that drains the North American Rocky Mountains and provides an international focus for water sharing. For ETP, we analysed monthly discharges from 1912 to 2008 with non‐parametric regression, and extrapolated changes to 2055. For modelling, we refined the physical models MTCLIM and SNOPAC to provide water inputs into RIVRQ (river discharge), a model that assesses the streamflow regime as involving dynamic peaks superimposed on stable baseflow. After parameterization with 1960–1989 data, we assessed climate forecasts from six GCMs: CGCM1‐A, HadCM3, NCAR‐CCM3, ECHAM4 and 5 and GCM2. Modelling reasonably reconstructed monthly hydrographs (R² about 0·7), and averaging over three decades closely reconstructed the monthly pattern (R² = 0·94). When applied to the GCM forecasts, the model predicted that summer flows would decline considerably, while winter and early spring flows would increase, producing a slight decline in the annual discharge (?3%, 2005–2055). The ETP predicted similarly decreased summer flows but slight change in winter flows and greater annual flow reduction (?9%). The partial convergence of the seasonal flow projections increases confidence in a composite analysis and we thus predict further declines in summer (about ? 15%) and annual flows (about ? 5%). This composite projection indicates a more modest change than had been anticipated based on earlier GCM analyses or trend projections that considered only three or four decades. For other river basins, we recommend the utilization of ETP based on the longest available streamflow records, and HCM with multiple GCMs. The degree of correspondence from these two independent approaches would provide a basis for assessing the confidence in projections for future river flows and surface water supplies. Copyright © 2010 John Wiley & Sons, Ltd.     

Selection and quality assessment of Landsat data for the North American forest dynamics forest history maps of the US

Using the NASA Earth Exchange platform, the North American Forest Dynamics (NAFD) project mapped forest history wall-to-wall, annually for the contiguous US (1986–2010) using the Vegetation Change Tracker algorithm. As with any effort to identify real changes in remotely sensed time-series, data gaps, shifts in seasonality, misregistration, inconsistent radiometry and cloud contamination can be sources of error. We discuss the NAFD image selection and processing stream (NISPS) that was designed to minimize these sources of error. The NISPS image quality assessments highlighted issues with the Landsat archive and metadata including inadequate georegistration, unreliability of the pre-2009 L5 cloud cover assessments algorithm, missing growing-season imagery and paucity of clear views. Assessment maps of Landsat 5–7 image quantities and qualities are presented that offer novel perspectives on the growing-season archive considered for this study. Over 150,000+ Landsat images were considered for the NAFD project. Optimally, one high quality cloud-free image in each year or a total of 12,152 images would be used. However, to accommodate data gaps and cloud/shadow contamination 23,338 images were needed. In 220 specific path-row image years no acceptable images were found resulting in data gaps in the annual national map products.