Nanocrystalline iron hydroxide lignocellulose filters for arsenate remediation.

Harmful levels of environmental contaminants, such as arsenic (As), persist readily in the environment, threatening safe drinking water supplies in many parts of the world. In this paper, we present a straightforward and cost-effective filtration technology for the removal of arsenate from potable water. Biocomposite filters comprised of nanocrystalline iron oxides or oxyhydroxides mineralized within lignocellulose scaffolds constitute a promising low cost, low-tech avenue for the removal of these contaminants. Two types of iron oxide mineral phases, 2-line ferrihydrite (Fh) and magnetite (Mt), were synthesized within highly porous balsa wood using an environmentally benign modification process and studied in view of their effective removal of As from contaminated water. The mineral deposition pattern, minerology, as well as crystallinity, were assessed using scanning electron microscopy, transmission electron microscopy, micro-computed X-ray tomography, confocal Raman microscopy, infrared spectroscopy, and X-ray powder diffraction. Our results indicate a preferential distribution of the Fh mineral phase within the micro-porous cell wall and radial parenchyma cells of rays, while Mt is formed primarily at the cell wall/lumen interface of vessels and fibers. Water samples of known As concentrations were subjected to composite filters in batch incubation and gravity-driven flow-through adsorption tests. Eluents were analyzed using microwave plasma optical emission spectroscopy (MP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). By subjecting the filters to a flow of contaminated water, the time for As uptake was reduced to minutes rather than hours, while immobilizing the same amount of As. The retention of As within the composite filter was further confirmed through energy-dispersive X-ray mappings. Apart from addressing dangerously high levels of arsenate in potable water, these versatile iron oxide lignocellulosic filters harbor tremendous potential for addressing current and emerging environmental contaminants that are known to adsorb on iron oxide mineral phases, such as phosphate, polycyclic aromatic hydrocarbons or heavy metals.

Synchrotron-based X-ray fluorescence microscopy mapping the ionome of a toxic freshwater cyanobacterium.

Harmful algal blooms (HABs) pose a major environmental concern across the globe. In abundance, cyanobacteria, or so-called green-blue algae can produce extremely dangerous cyanotoxins that harm humans and animals. This study focused on the mapping and distribution of intracellular macro-and micronutrients of the wide-spread freshwater cyanobacteria Microcystis aeruginosa (M. aeruginosa). Towards a better understanding of trace metal uptake and homeostasis throughout the cell cycle, we quantitatively mapped the spatial distribution of the elements P, K, Fe, Ca, Zn, Mn, and Cu across the ultrastructure of frozen-hydrated single cells using state-of-the-art X-ray nanofluorescence imaging at the Advanced Photon Source (APS) at Argonne National Laboratory. Bulk cellular nutrient and trace metal content correlated well with the total intracellular elemental content in individual cells obtained by quantitative synchrotron X-ray fluorescence measurements. Multi-dimensional mappings showed P and K atoms colocalized as discrete semicircular hotspots that were analyzed with respect to their stoichiometry. Elevated Cu and Ca concentrations were detected along division plane of cells. P and K were found to have similar spatial elemental distribution with about 65% and 69% of the total cellular P and K, respectively, located at the hotspots. The P and K colocalization were refined further using nanotomography, showing a K envelope surrounding the P core. Inorganic P and organic P compounds were specified using solution-state 31P nuclear magnetic resonance (NMR) spectroscopy from M. aeruginosa. Of the total extracted P determined by 31P NMR spectroscopy, 47% were found to be nucleotides while only 11% were polyphosphates. Multimodal X-ray imaging provides a better understanding of intracellular biochemical processes in cyanobacteria, helping us monitor and combat an emerging environmental threat.

Phosphorus retention within a relic agricultural ditch in a constructed wetland.

Stormwater treatment areas (STAs) are constructed wetlands established to capture phosphorus (P) from agricultural runoff before reaching the Florida Everglades. Retained P is primarily stored in wetland soils and sediments generated through a collection of interrelated physical, chemical, and biological processes. The amount of P and other elements (Al, Ca, Cu, Fe, Mg, Mn, Pb, and Zn) retained in the flocculent (floc) and recently accreted soil (RAS) horizons from a relic agricultural ditch within Cell 4S of STA-1E were compared with the surrounding marsh soils (upstream and downstream sites of the ditch). The amount of P retained in the ditch was significantly greater than the surrounding marsh soils and for all the elements in the floc horizon and five of the nine elements in the RAS horizon, suggesting that different processes or process rates influenced accumulation. Phosphorus species in the floc and RAS sediment horizons were identified and quantified using 31 P nuclear magnetic resonance (NMR) spectroscopy and total P determined by microwave plasma-optical emission spectroscopy. In general, P forms were dominated by orthophosphate, sugar phosphates, nucleotides, DNA, and pyrophosphate, with varying relative abundances of species. Total P concentration significantly decreased from upstream to downstream of the ditch by an average of 28 and 35% for floc and RAS soils, respectively. The relatively high P accrual rate within the ditch suggested that relic ditches perpendicular to flow could reduce P transport to downstream soils and sediments and, in turn, help maintain low P levels in overlying water.

The role of rice (Oryza sativa L.) in sequestering phosphorus compounds and trace elements: Speciation and dynamics.

In southern Florida, the sequestering of nutrients through the cultivation of rice (Oryza sativa L.) in alternation with sugarcane (Saccharum spp.) crops is an essential step in minimizing downstream eutrophication of the Florida Everglades. Phosphorus (P) is known to be the leading cause of this eutrophication; however, the cultivation/harvesting of rice effectively reduces P and additional macro and micro-nutrients from agrarian soil and runoff through plant uptake. In this study, soil, water, sugarcane, and rice plants at two different stages (flooded and vegetative) were analyzed for twelve different elements (Al, As, Co, Cr, Cu, Fe, Ni, Zn, Ca, Mn, Mg, and P) by Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES). 31P Nuclear Magnetic Resonance (NMR) spectra of the rice plants confirmed ten different P compounds being transported and/or transformed throughout the entirety of the sugarcane and rice plants. On average, dried rice plants contained 1677 ± 14 mg-P, of which 1277 ± 3.0 mg-P was in the panicle at the vegetative stage. Harvesting of the rice panicle has the potential to remove about 14.7 kg-P/ha for the top 10 cm of the soil. This present study demonstrates that in rotations with sugarcane crops and with no added P fertilizer, rice cultivation can reduce considerable amounts of P that would otherwise leach into the Greater Everglades from the Everglades Agricultural Area.