Letuzia M. de Oliveira

Mechanisms of metal sorption by biochars: Biochar characteristics and modifications

Biochar produced by thermal decomposition of biomass under oxygen-limited conditions has received increasing attention as a cost-effective sorbent to treat metal-contaminated waters. However, there is a lack of information on the roles of different sorption mechanisms for different metals and recent development of biochar modification to enhance metal sorption capacity, which is critical for biochar field application. This review summarizes the characteristics of biochar (e.g., surface area, porosity, pH, surface charge, functional groups, and mineral components) and main mechanisms governing sorption of As, Cr, Cd, Pb, and Hg by biochar. Biochar properties vary considerably with feedstock material and pyrolysis temperature, with high temperature producing biochars with higher surface area, porosity, pH, and mineral contents, but less functional groups. Different mechanisms dominate sorption of As (complexation and electrostatic interactions), Cr (electrostatic interactions, reduction, and complexation), Cd and Pb (complexation, cation exchange, and precipitation), and Hg (complexation and reduction). Besides sorption mechanisms, recent advance in modifying biochar by loading with minerals, reductants, organic functional groups, and nanoparticles, and activation with alkali solution to enhance metal sorption capacity is discussed. Future research needs for field application of biochar include competitive sorption mechanisms of co-existing metals, biochar reuse, and cost reduction of biochar production.

Bacteria-Mediated Arsenic Oxidation and Reduction in the Growth Media of Arsenic Hyperaccumulator Pteris vittata

Microbes play an important role in arsenic transformation and cycling in the environment. Microbial arsenic oxidation and reduction were demonstrated in the growth media of arsenic hyperaccumulator Pteris vittata L. All arsenite (AsIII) at 0.1 mM in the media was oxidized after 48 h incubation. Oxidation was largely inhibited by antibiotics, indicating that bacteria played a dominant role. To identify AsIII oxidizing bacteria, degenerate primers were used to amplify ∼500 bp of the AsIII oxidase gene aioA (aroA) using DNA extracted from the media. One aioA (aroA)-like sequence (MG-1, tentatively identified as Acinetobacter sp.) was amplified, exhibiting 82% and 91% identity in terms of gene and deduced protein sequence to those from Acinetobacter sp. 33. In addition, four bacterial strains with different arsenic tolerance were isolated and identified as Comamonas sp.C-1, Flavobacterium sp. C-2, Staphylococcus sp. C-3, and Pseudomonas sp. C-4 using carbon utilization, fatty acid profiles, and/or sequencing 16s rRNA gene. These isolates exhibited dual capacity for both AsV reduction and AsIII oxidation under ambient conditions. Arsenic-resistant bacteria with strong AsIII oxidizing ability may have potential to improve bioremediation of AsIII-contaminated water using P. vittata and/or other biochemical strategies.

Antimony uptake, efflux and speciation in arsenic hyperaccumulator Pteris vittata.

Even though antimony (Sb) and arsenic (As) are chemical analogs, differences exist on how they are taken up and translocated in plants. We investigated 1) Sb uptake, efflux and speciation in arsenic hyperaccumulator Pteris vittata after 1 d exposure to 1.6 or 8 mg/L antimonite (SbIII) or antimonate (SbV), 2) Sb uptake by PV accessions from Florida, China, and Brazil after 7 d exposure to 8 mg/L SbIII, and 3) Sb uptake and oxidation by excised PV fronds after 1 d exposure to 8 mg/L SbIII or SbV. After 1 d exposure, P. vittata took 23-32 times more SbIII than SbV, with all Sb being accumulated in the roots with the highest at 4,192 mg/kg. When exposed to 8 mg/L SbV, 98% of Sb existed as SbV in the roots. In comparison, when exposed to 8 mg/L SbIII, 81% of the total Sb remained as SbIII and 26% of the total Sb was effluxed out into the media. The three PV accessions had a similar ability to accumulate Sb at 12,000 mg/kg in the roots, with >99% of total Sb in the roots. Excised PV fronds translocated SbV more efficiently from the petioles to pinnae than SbIII and were unable to oxidize SbIII. Overall, P. vittata displayed efficient root uptake and efflux of SbIII with limited ability to translocate and transform in the roots.

Arsenic-hyperaccumulator Pteris vittata efficiently solubilized phosphate rock to sustain plant growth and As uptake

Phosphorus (P) is one of the most important nutrients for phytoremediation of arsenic (As)-contaminated soils. In this study, we demonstrated that As-hyperaccumulator Pteris vittata was efficient in acquiring P from insoluble phosphate rock (PR). When supplemented with PR as the sole P source in hydroponic systems, P. vittata accumulated 49% and 28% higher P in the roots and fronds than the -P treatment. In contrast, non-hyperaccumulator Pteris ensiformis was unable to solubilize P from PR. To gain insights into PR solubilization by plants, organic acids in plant root exudates were analyzed by HPLC. The results showed that phytic acid was the predominant (>90%) organic acid in P. vittata root exudates whereas only oxalic acid was detected in P. ensiformis. Moreover, P. vittata secreted more phytic acid in -P and PR treatments. Compared to oxalic acid, phytic acid was more effective in solubilizing PR, suggesting that phytic acid was critical for PR utilization. Besides, secretion of phytic acid by P. vittata was not inhibited by arsenate. Our data indicated that phytic acid played an important role in efficient use of insoluble PR by P. vittata, shedding light on using insoluble PR to enhance phytoremediation of As-contaminated soils.

Chromate and phosphate inhibited each other's uptake and translocation in arsenic hyperaccumulator Pteris vittata L.

We investigated the effects of chromate (CrVI) and phosphate (P) on their uptake and translocation in As-hyperaccumulator Pteris vittata (PV). Plants were exposed to 1) 0.10 mM CrVI and 0, 0.25, 1.25, or 2.50 mM P or 2) 0.25 mM P and 0, 0.50, 2.5 or 5.0 mM CrVI for 24 h in hydroponics. PV accumulated 2919 mg/kg Cr in the roots at CrVI₀.₁₀, and 5100 and 3500 mg/kg P in the fronds and roots at P₀.₂₅. When co-present, CrVI and P inhibited each others uptake in PV. Increasing P concentrations reduced Cr root concentrations by 62-82% whereas increasing CrVI concentrations reduced frond P concentrations by 52-59% but increased root P concentrations by 11-15%. Chromate reduced P transport, with more P being accumulated in PV roots. Though CrVI was supplied, 64-78% and 92-93% CrIII were in PV fronds and roots. Based on X-ray diffraction, Cr₂O₃ was detected in the roots confirming CrVI reduction to CrIII by PV. In short, CrVI and P inhibited each other in uptake and translocation by PV, and CrVI reduction to CrIII in PV roots served as its detoxification mechanism. The finding helps to understand the interactions of P and Cr during their uptake in PV.

Sulfate and chromate increased each other's uptake and translocation in As-hyperaccumulator Pteris vittata

We investigated the effects of chromate (CrVI) and sulfate on their uptake and translocation in As-hyperaccumulator Pteris vittata. Plants were exposed to 1) 0.1 mM CrVI and 0, 0.25, 1.25 or 2.5 mM sulfate or 2) 0.25 mM sulfate and 0, 0.5, 2.5 or 5.0 mM CrVI for 1 d in hydroponics. P. vittata accumulated 26 and 1261 mg kg(-1) Cr in the fronds and roots at CrVI0.1, and 2197 and 1589 mg kg(-1) S in the fronds and roots at S0.25. Increasing sulfate concentrations increased Cr root concentrations by 16-66% and helped CrVI reduction to CrIII whereas increasing CrVI concentrations increased frond sulfate concentrations by 3-27%. Increasing sulfate concentrations enhanced TBARS concentrations in the biomass, indicating oxidative stress caused lipid peroxidation in plant cell membranes. However, addition of 0.25-2.5 mM sulfate alleviated CrVIs toxic effects and decreased TBARS from 23.5 to 9.46-12.3 μmol g(-1) FW. Though CrVI was supplied, 78-96% of CrIII was in the biomass, indicating efficient CrVI reduction to CrIII by P. vittata. The data indicated the amazing ability of P. vittata in Cr uptake at 289 mg kg(-1) h(-1) with little translocation to the fronds. These results indicated that P. vittata had potential in Cr phytoremediation in contaminated sites but further studies are needed to evaluate this potential. The facts that CrVI and sulfate helped each other in uptake by P. vittata suggest that CrVI was not competing with sulfate uptake in P. vittata. However, the mechanisms of how sulfate and CrVI enhance each others accumulation in P. vittata need further investigation.

Antioxidant enzymes responses in shoots of arsenic hyperaccumulator, Isatis cappadocica Desv., under interaction of arsenate and phosphate

ABSTRACT The present study investigated the effects of arsenate and phosphate interaction on growth, lipid peroxidation, arsenic (As) accumulation, phosphorus (P) accumulation, and the activities of some antioxidant enzymes in Isatis cappadocica. Plants were exposed to (50–1200 μmol L−1) arsenate and (5–1600 μmol L−1) phosphate for 28 days in a hydroponic system. At a phosphate concentration of 1600 µM, biomass production and chlorophyll content increased, demonstrating clearly that phosphate was able to provide protection against As toxicity. In case of joint application of 1600 µM phosphate with arsenate, the As accumulation and then lipid peroxidation were decreased when compared to samples treated with arsenate and 5 µM phosphate. The activities of superoxide dismutase (SOD), ascorbate peroxidase (APX), catalase (CAT) and glutathione reductase (GR) increased with increasing arsenate supply levels. Addition of P decreased activities of SOD, APX and CAT, while high phosphate treatments had a positive effect on GR activity, which may be due to regulation of glutathione biosynthesis within the plants. In conclusion, high arsenate treatment (800-1200 µM) could cause an increasing oxidative stress, which can be scavenged by the antioxidant enzyme. Furthermore, P may affect As-induced oxidative stress through nutrient condition and As accumulation. GRAPHICAL ABSTRACT

Metal leachability from coal combustion residuals under different pHs and liquid/solid ratios

Coal combustion residuals (CCRs) contain variable amounts of trace metals, which can negatively impact the environment. We analyzed metal concentrations and leachability of CCRs from seven coal-fired power plants from Florida. The purpose of this study was to characterize and assess metal leachability in representative CCRs samples from coal-fired power plants, including As, Ba, Cd, Cr, Pb, and Se. The specific objectives were to: (1) measure metal leachability under different pH conditions and liquid-to-solid ratios using USEPA Leaching Environmental Assessment Framework (LEAF) Methods 1313 and 1316, and (2) compare their leachability with those obtained by the Synthetic Precipitation Leaching Procedure (SPLP). All metals excluding Cd showed amphoteric behavior, presenting higher concentrations at low and high pH using LEAF Method 1313. The highest Cd leaching was observed at pH 2-4 and decreased at pH>7. SPLP results were highly variable when compared to the LEAF data. All metals except Ba exceeded the Florida Groundwater Cleanup Target Levels at all pH levels, however, metal leaching was low at typical soil pH of 4-9. Metal concentrations in fly ash decreased in most cases with increasing LS ratio. Therefore, due to potential leaching of some metals, evaluation is needed before beneficial use of CCRs.

Metal concentrations in traditional and herbal teas and their potential risks to human health

Food and beverage consumption is an important route for human exposure to metals. Traditional tea (Camellia sinensis) is a widely-consumed beverage, which may contain toxic metals. This study determined total and infusion concentrations of 5 metals including Al, As, Cd, Cr, and Pb in 47 traditional and herbal teas from 13 countries and assessed their potential risks to human health. The data showed that herbal teas exhibited higher As (0.26mgkg-1), Cd (0.19mgkg-1) and Pb (2.32mgkg-1) than traditional teas. Black tea from India had high Cr at 31mgkg-1 while white tea from China had low Cr at 0.39mgkg-1. Arsenic, Cd and Pb did not exceed the WHO limit for medicinal plants excluding one herbal tea with 1.1mgkg-1 As and 26.4mgkg-1 Pb. However, Cr in 47% herbal teas and 73% traditional teas exceeded the Canada limit of 2mgkg-1. Metal concentrations in tea infusions were below the MCL for drinking water except for Al. Total Al and its infusion was lower in herbal teas (47-1745mgkg-1 and 0.09-3.95mgL-1) than traditional teas (50.3-2517mgkg-1 and 0.02-7.51mgL-1), with 0.9-22% and 4-49% of the Al being soluble in infusion. The Al concentrations in infusion in all black tea and 83, 75 and 25% of the green, oolong and herbal teas exceeded the secondary MCL for drinking water at 0.2mgL-1. However, the weekly intake of Al from drinking tea (0.001-0.39 and 0.003-0.56mgkg-1 for children and adults) was lower than the provisional tolerable weekly intake for Al at 1.0mgkg-1. Our data showed that it is important to consider metal intake from tea consumptions, especially for Cr and Al in heavy tea drinkers.

Interactive effects of chromate and arsenate on their uptake and speciation in Pteris ensiformis

Background and aimsArsenate (AsV) and chromate (CrVI) inhibit each other’s uptake and translocation in As-hyperaccumulator Pteris vittata. In the present study, we extended the research to As-sensitive plant Pteris ensiformis to better understand the mechanism of their interactions.MethodsPlants were exposed to 0, 0.75 or 7.5 mg L−1 AsV and 0, 0.52, or 5.2 mg L−1 CrVI for 7 d in hydroponics. Arsenic and Cr speciation were determined in nutrient solutions and plant biomass.ResultsP. ensiformis accumulated high levels of As and Cr in the rhizomes and roots with low levels in the fronds. However, P. ensiformis was much more effective in taking up Cr than As, as much more Cr was accumulated in the roots (306–6015 vs. 87–642 mg kg−1). AsV and CrVI increased each other’s uptake in the rhizomes and roots when co-present. The AsV and CrVI taken up by P. ensiformis were reduced to arsenite (AsIII) and chromite (CrIII), possibly serving as detoxification mechanism.ConclusionsUptake of As and Cr induced oxidative stress as indicated by increased lipid peroxidation and electrical conductivity. Arsenic and Cr increased each other’s uptake by P. ensiformis.