Lena Q. Ma

A fern that hyperaccumulates arsenic

A hardy, versatile, fast-growing plant helps to remove arsenic from contaminated soils.

Arsenic speciation and distribution in an arsenic hyperaccumulating plant

Arsenic-contaminated soil is one of the major arsenic sources for drinking water. Phytoremediation, an emerging, plant-based technology for the removal of toxic contaminants from soil and water, has been receiving renewed attention. Although a number of plants have been identified as hyperaccumulators for the phytoextraction of a variety of metals, and some have been used in field applications, no hyperaccumulator for arsenic had been previously reported until the recent discovery of Brake fern (Pteris vittata), which can hyperaccumulate arsenic from soils. This finding may open a door for phytoremediation of arsenic-contaminated soils. Speciation and distribution of arsenic in the plant can provide important information helpful to understanding the mechanisms for arsenic accumulation, translocation, and transformation. In this study, plant samples after 20 weeks of growth in an arsenic-contaminated soil were used for arsenic speciation and distribution study. A mixture of methanol/water (1:1) was used to extract arsenic compounds from the plant tissue. Recoveries of 85 to 100% were obtained for most parts of the plant (rhizomes, fiddle heads, young fronds and old fronds) except for roots, for which extraction efficiency was approximately 60%. The results of this study demonstrate the ability of Brake fern as an arsenic hyperaccumulator. It transfers arsenic rapidly from soil to aboveground biomass with only minimal arsenic concentration in the roots. The arsenic is found to be predominantly as inorganic species; and it was hypothesized that the plant uptakes arsenic as arsenate [As(V)I and arsenate was converted to arsenite [As(III)] within the plant. The mechanisms of arsenic uptake, translocation, and transformation by this plant are not known and are the objectives of our on-going research.

Mechanisms of Lead, Copper, and Zinc Retention by Phosphate Rock

The solid-liquid interface reaction between phosphate rock (PR) and metals (Pb, Cu, and Zn) was studied. Phosphate rock has the highest affinity for Pb, followed by Cu and Zn, with sorption capacities of 138, 114, and 83.2 mmol/kg PR, respectively. In the Pb-Cu-Zn ternary system, competitive metal sorption occurred with sorption capacity reduction of 15.2%, 48.3%, and 75.6% for Pb, Cu, and Zn, respectively compared to the mono-metal systems. A fractional factorial design showed the interfering effect in the order of Pb>Cu>Zn. Desorption of Cu and Zn was sensitive to pH change, increasing with pH decline, whereas Pb desorption was decreased with a strongly acidic TCLP extracting solution (pH = 2.93). The greatest stability of Pb retention by PR can be attributed to the formation of insoluble fluoropyromorphite [Pb(10)(PO(4))(6)F(2)], which was primarily responsible for Pb immobilization (up to 78.3%), with less contribution from the surface adsorption or complexation (21.7%), compared to 74.5% for Cu and 95.7% for Zn. Solution pH reduction during metal retention and flow calorimetry analysis both supported the hypothesis of retention of Pb, Cu, and Zn by surface adsorption or complexation. Flow calorimetry indicated that Pb and Cu adsorption onto PR was exothermic, while Zn sorption was endothermic. Our research demonstrated that PR can effectively remove Pb from solutions, even in the presence of other heavy metals (e.g. Cu, Zn).

Simultaneous Immobilization of Lead and Atrazine in Contaminated Soils Using Dairy-Manure Biochar

Biochar produced from waste biomass is increasingly being recognized as a green, cost-effective amendment for environmental remediation. This work was to determine the ability of biochar to immobilize heavy metal Pb and organic pesticide atrazine in contaminated soils. Biochar prepared from dairy manure was incubated with contaminated soils at rates of 0, 2.5, and 5.0% by weight for 210 d. A commercial activated carbon (AC) was included as a comparison. The AC was effective in immobilizing atrazine, but was ineffective for Pb. However, biochar was effective in immobilizing both atrazine and Pb and the effectiveness was enhanced with increasing incubation time and biochar rates. After 210 d, soils treated with the highest rate of 5.0% biochar showed more than 57% and 66% reduction in Pb and atrazine concentrations in 0.01 M CaCl(2) extraction, respectively. Lead and atrazine concentrations in the toxicity characteristic leaching procedure solutions were reduced by 70-89% and 53-77%, respectively. Uptake of Pb and atrazine by earthworms (Eisenia fetida) was reduced by up to 79% and 73%. Phosphorus originally contained in biochar reacted with soil Pb to form insoluble hydroxypyromorphite Pb(5)(PO(4))(3)(OH), as determined by X-ray diffraction, which was presumably responsible for soil Pb immobilization, whereas atrazine stabilization may result from its adsorption by biochar demonstrated by the significant exponential decrease of extractable atrazine with increasing organic C in biochar (r(2) > 0.97, p < 0.05). The results highlighted the potential of dairy-manure biochar as a unique amendment for immobilization of both heavy metal and organic contaminants in cocontaminated soils.

Phosphate-induced metal immobilization in a contaminated site

To assess the efficiency of P-induced metal immobilization in soils, a pilot-scale field experiment was conducted at a metal contaminated site located in central Florida. Phosphate was applied at a P/Pb molar ratio of 4.0 with three treatments: 100% of P from H3PO4, 50% of P from H3PO4+ 50% of P from Ca(H2PO4)2, and 50% of P from H3PO4+5% phosphate rock in the soil. Approximately 1 year after P application, soil and plant samples were collected to determine mobility and bioavailability of selected metals (Pb, Zn, and Cu) using sequential extraction procedure and mineralogical characterization using X-ray diffraction (XRD) and scanning electron microscope-energy dispersive X-ray (SEM-EDX) analysis. Phosphorus distribution and soil pH effects were also evaluated. Phosphate was more effective in transforming soil Pb (to 53%) from the non-residual to the residual phase than soil Zn (to 15%) and soil Cu (to 13%). This was because Pb was immobilized by P via formation of an insoluble pyromorphite-like mineral in the surface and subsurface of the soil, whereas no phosphate mineral Zn or Cu was identified. While P amendment enhanced metal uptake in the roots of St. Augustine grass (Stenotaphrum secundatum), it significantly reduced metal translocation from root to shoot, especially Pb via formation of a pyromorphite-like mineral on the membrane surface of the root. A mixture of H3PO4 and phosphate rock was effective in metal immobilization, with less soil pH reduction and less soluble P. Although H3PO4 was effective in immobilizing Pb, its use should be limited to minimize soil pH reduction and potential eutrophication risk.

Effects of Arsenic Concentrations and Forms on Arsenic Uptake by the Hyperaccumulator Ladder Brake

Ladder brake (Pteris vittata L.) is a newly discovered arsenic hyperaccumulator. No information is available about arsenic effects on ladder brake. This study determined the effects of different arsenic concentrations (50 to 1000 mg kg(-1)) or forms (organic vs. inorganic and arsenite vs. arsenate) applied to soils on growth and arsenic uptake by ladder brake. Young plants were grown in a greenhouse for 12 or 18 wk. Ladder brake was highly tolerant of arsenic and survived in soil containing up to 500 mg As kg(-1). The fact that addition of arsenate up to 100 mg As kg(-1) increased fern biomass by 64 to 107%, coupled with higher arsenic concentration in younger fronds at low soil arsenic concentrations and older fronds at high soil arsenic concentrations, implies that arsenic may be beneficial for fern growth. Addition of 50 mg As kg(-1) was best for fern growth and arsenic accumulation, resulting in the highest fern biomass (3.9 g plant(-1)), bioconcentration factor (up to 63), and translocation factor (up to 25). With an exception of FeAsO4 and AlAsO4, which had the lowest effects due to their low solubility, little difference was observed among other arsenic forms mainly because of arsenic conversion in soil. Aboveground biomass was mostly responsible for accumulation of arsenic by plant (75-99%). Up to 26% of the added arsenic was removed by ladder brake, showing the high efficiency of ladder brake in arsenic removal. The results suggest that ladder brake may be a good candidate to remediate arsenic-contaminated soils.

Immobilization of Zn, Cu, and Pb in contaminated soils using phosphate rock and phosphoric acid

Considerable research has been done on P-induced Pb immobilization in Pb-contaminated soils. However, application of P to soils contaminated with multiple heavy metals is limited. The present study examined effectiveness of phosphoric acid (PA) and/or phosphate rock (PR) in immobilizing Pb, Cu, and Zn in two contaminated soils. The effectiveness was evaluated using water extraction, plant uptake, and a simple bioaccessibility extraction test (SBET) mimicking metal uptake in the acidic environment of human stomach. The possible mechanisms for metal immobilization were elucidated using X-ray diffraction, scanning electron microscopy, and chemical speciation program Visual MINTEQ. Compared to the control, all P amendments significantly reduced Pb water solubility, phytoavailability, and bioaccessibility by 72-100%, 15-86%, and 28-92%, respectively. The Pb immobilization was probably attributed to the formation of insoluble Pb phosphate minerals. Phosphorus significantly reduced Cu and Zn water solubility by 31-80% and 40-69%, respectively, presumably due to their sorption on minerals (e.g., calcite and phosphate phases) following CaO addition. However, P had little effect on the Cu and Zn phytoavailability; while the acid extractability of Cu and Zn induced by SBET (pH 2) were even elevated by up to 48% and 40%, respectively, in the H(3)PO(4) treatments (PA and PR+PA). Our results indicate that phosphate was effective in reducing Pb availability in terms of water solubility, bioaccessibility, and phytoavailability. Caution should be exercised when H(3)PO(4) was amended to the soil co-contaminated with Cu and Zn since the acidic condition of SBET increased Cu and Zn bioaccessibility though their water solubility was reduced.

Effects of compost and phosphate amendments on arsenic mobility in soils and arsenic uptake by the hyperaccumulator, Pteris vittata L.

Chinese brake fern (Pteris vittata L.), an arsenic (As) hyperaccumulator, has shown the potential to remediate As-contaminated soils. This study investigated the effects of soil amendments on the leachability of As from soils and As uptake by Chinese brake fern. The ferns were grown for 12 weeks in a chromated-copper-arsenate (CCA) contaminated soil or in As spiked contaminated (ASC) soil. Soils were treated with phosphate rock, municipal solid waste, or biosolid compost. Phosphate amendments significantly enhanced plant As uptake from the two tested soils with frond As concentrations increasing up to 265% relative to the control. After 12 weeks, plants grown in phosphate-amended soil removed >8% of soil As. Replacement of As by P from the soil binding sites was responsible for the enhanced mobility of As and subsequent increased plant uptake. Compost additions facilitated As uptake from the CCA soil, but decreased As uptake from the ASC soil. Elevated As uptake in the compost-treated CCA soil was related to the increase of soil water-soluble As and As(V) transformation into As(III). Reduced As uptake in the ASC soil may be attributed to As adsorption to the compost. Chinese brake fern took up As mainly from the iron-bound fraction in the CCA soil and from the water-soluble/exchangeable As in the ASC soil. Without ferns for As adsorption, compost and phosphate amendments increased As leaching from the CCA soil, but had decreased leaching with ferns when compared to the control. For the ASC soil, treatments reduced As leaching regardless of fern presence. This study suggest that growing Chinese brake fern in conjunction with phosphate amendments increases the effectiveness of remediating As-contaminated soils, by increasing As uptake and decreasing As leaching.

Point of zero charge determination in soils and minerals via traditional methods and detection of electroacoustic mobility

Points of zero charge were determined on two highly weathered surface soils from Puerto Rico, an Oxisol and Ultisol, as well as mineral-standard kaolinite and synthetic goethite using three methods: (1) potentiometric titration measuring the adsorption of H+ and OH− on amphoteric surfaces in solutions of varying ionic strength (I) (point of zero salt effect), (2) direct assessment of surface charges via non-specific ion adsorption as a function of pH and I (point of zero net charge), and (3) electroacoustic mobility of reversible particles as it varies with pH and I (isoelectric point). The first two methods yielded points of zero charge for kaolinite (2.7–3.2) and synthetic goethite (7.4–8.2) comparable to those reported previously, indicating the reliability of these analyses. The soil values ranged from 3.9 to 4.4 for the Oxisol and 2.3 to 3.7 for the Ultisol. Electroacoustic mobility, as measured by the AcoustoSizer™, is a parameter that has yet to be thoroughly tested for mineral or soil systems as a viable alternative to PZC assessment. The points of zero charge from electroacoustic mobility of kaolinite (3.8–4.1) and synthetic goethite (8.1–8.2) were similar to values obtained by electrophoretic mobility. Furthermore, the values found for the Oxisol (3.4–3.5) and Ultisol (2.6–2.7) were in the range expected for these soils.

Characteristics and mechanisms of hexavalent chromium removal by biochar from sugar beet tailing

Removal of Cr(VI) from aqueous solutions using biochar from sugar beet tailing (SBT) was investigated as a function of pH, contact time, and biochar mass via batch experiments. The surface characteristics of SBT biochar before and after Cr(VI) sorption was investigated with scanning electron microscopy equipped with energy dispersive X-ray spectroscopy and Fourier transform infrared spectroscopy. Desorption and X-ray photoelectron spectroscopy studies showed that most of the Cr bound to SBT biochar was Cr(III). These results indicated that the electrostatic attraction of Cr(VI) to positively charged biochar surface, reduction of Cr(VI) to Cr(III) ion, and complexation between Cr(III) ion and SBTs function groups were probably responsible for Cr(VI) removal by SBT biochar. An initial solution with a pH of 2.0 was most favorable for Cr(VI) removal. The sorption process can be described by the pseudo-second order equation and Langmuir isotherm. The maximum sorption capacity for Cr(VI) was 123 mg/g under an acidic medium, which was comparable to other low-cost sorbents.