Effects of copper and arsenic on their uptake and distribution in As-hyperaccumulator Pteris vittata.

Arsenic (As) and copper (Cu) are common co-contaminates in soils. However, their interactive effects on their accumulation and distribution in As-hyperaccumulator Pteris vittata are poorly understood. A hydroponic experiment was conducted with As being 0, 5, or 50 µM and Cu being 0.32, 3.2, or 32 µM to evaluate their phytotoxicity, accumulation, and distribution in P. vittata. In addition, As and Cu uptake kinetics were examined using the Michaelis-Menten kinetics model. Total As and Cu concentrations in P. vittata were up to 487 and 1355 mg kg-1. About 39-81% of the As was in the fronds compared to 0.6-18% for Cu. At 50 µM As, increasing Cu concentration from 0.32 to 32 µM increased root As while decreasing frond As concentrations, with the translocation factor (ratio of As in fronds to roots) being reduced from 4.0 to 0.31. In contrast, As did not affect Cu accumulation in P. vittata. Michaelis constant Km value for As was higher than that of Cu (6.49-24.9 vs. 0.43-3.36), consistent with higher Cu uptake than As. Besides, Cu reduced root K but increased P levels in the roots, whereas As increased the K and P concentrations in the fronds. Our results suggest that P. vittata accumulated more Cu than As in the roots, contributing to its low As translocation. As such, high levels of Cu are likely to reduce As uptake by P. vittata during phytoremediation of As-contaminated sites.

Background concentrations of trace metals As, Ba, Cd, Co, Cu, Ni, Pb, Se, and Zn in 214 Florida urban soils: Different cities and land uses.

Soil contamination in urban environment by trace metals is of public concerns. For better risk assessment, it is important to determine their background concentrations in urban soils. For this study, we determined the background concentrations of 9 trace metals including As, Ba, Cd, Co, Cu, Ni, Pb, Se, and Zn in 214 urban soils in Florida from two large cities (Orlando and Tampa) and 4 small cities (Clay County, Ocala, Pensacola and West Palm Beach). The objectives were to determine: 1) total concentrations of trace metals in urban soils in cities of different size; 2) compare background concentrations to Florida Soil Cleanup Target Levels (FSCTLs); and 3) determine their distribution and variability in urban soils via multivariate statistical analysis. Elemental concentrations in urban soils were variable, with Pb being the highest in 5 cities (165-552 mg kg-1) and Zn being the highest concentration in Tampa (1,000 mg kg-1). Besides, the As and Pb concentrations in some soils exceeded the FSCTL for residential sites at 2.1 mg kg-1 As and 400 mg kg-1 Pb. Among the cities, Clay County and Orlando had the lowest concentrations for most elements, with Cd, Co, and As being the lowest while Ba, Pb and Zn being the highest. Among all values, geometric means were the lowest while 95th percentile was the highest for all metals. Most 95th percentile values were 2-3 folds higher than the GM data, with Pb presenting the greatest difference, being 4 times greater than GM value (58.9 vs. 13.6 mg kg-1). Still they were lower than FSCTL, with As exceeding FSCTL for residential sites at 2.1 mg kg-1. In addition, the linear discriminate analysis showed distinct separation among the cities: Ocala (Ba & Ni) and Pensacola (As & Pb) were distinctly different from each other and from other cities with higher metal concentrations. The large variations among elemental concentrations showed the importance to establish proper background concentrations of trace metals in urban soils.

Emerging and legacy PAHs in urban soils of four small cities: Concentrations, distribution, and sources.

Polycyclic aromatic hydrocarbons (PAHs) are widespread organic contaminants in the environment, much being accumulated in soils. Although their concentrations in large cities have been studied, their levels in small cities were less studied. This study determined the concentrations, distributions, and sources of 16 USEPA priority PAHs (legacy PAHs) and 6 emerging PAHs in urban soils of four small cities. A total of 100 soil samples were collected in Florida, USA. The average ∑16-PAHs in urban soils of Clay county, Ocala, Pensacola, and West Palm Beach were 1821, 2748, 3115 and 4055 µg kg-1, respectively. Based on benzo[a]pyrene-equivalent (BaP-EQ), the 7 USEPA carcinogenic PAHs (7cPAHs) and 3 emerging carcinogenic PAHs (3cPAHs) in urban soils in Clay County averaged 223 and 3703, Ocala 319 and 4521, Pensacola 302 and 5423, and West Palm Beach 449 and 5916 µg kg-1, respectively. Although ∑7cPAHs in 87-89% of samples were lower than the Florida Soil Cleanup Target Levels (FSCTLs) for industrial sites at 700 µg kg-1, ∑3cPAHs were 13-18 times greater than ∑7cPAHs. Based on the PMF model and molecular diagnostic ratios, soil PAHs were dominated by similar sources in small cities, mainly from pyrogenic sources including biomass, coal and coke combustion and vehicle emissions. It is important to evaluate both legacy and emerging PAHs concentrations in urban soils when considering soil remediation and human health risk assessment.

Anaerobic digestion to reduce biomass and remove arsenic from As-hyperaccumulator Pteris vittata.

The lack of efficient methods to treat As-rich biomass is a drawback for phytoremediation technology. In this study, we applied anaerobic digestion to reduce biomass and remove As from As-rich Pteris vittata biomass. P. vittata biomass including control (3.1 mg kg-1 As) and As-rich (2665 mg kg-1 As), together with positive and negative controls, was anaerobically digested at 35 °C for 35 d. Arsenic partitioning among gas, liquid and solid phases after anaerobic digestion was determined. Methane index potential assay was used to assess methane yields whereas liquid-displacement method was used to measure methane gas production. After 35 d, As partitioning in the liquid, solid and gas phases was 79, 30 and 1%, respectively. Besides, volatile solid was decreased from 91 to 12-17% total solid, while P. vittata biomass was decreased by 73-83%. Moreover, anaerobic digestion solubilized 76% As from P. vittata biomass, with 90% soluble As at 4.95 mg L-1 being recovered by As-Mg precipitation. Finally, methane production after 35 d was 197-212 LNCH4/kg volatile solid, showing slight As inhibition. Effective As removal from P. vittata biomass prior to disposal can improve the phytoremediation process.

Emerging PAHs in urban soils: Concentrations, bioaccessibility, and spatial distribution.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous organic contaminants, with soil being the most important sink. This study determined the concentrations, bioaccessibility and spatial distributions of 6 emerging PAHs in Orlando and Tampa urban soils. They included 3 carcinogenic (anthanthrene, 7H-benzo[c]fluorene, and dibenzo[a,l]pyrene: 3cPAHs) and 3 non-carcinogenic (dibenzo[a,e]pyrene, dibenzo[a,i]pyrene and dibenzo[a,h]pyrene) PAHs. Based on benzo[a]pyrene-equivalent, the 7 USEPA priority cPAHs (7cPAHs) and 3cPAHs in Orlando soils averaged 452 and 7387 µg kg-1, and Tampa soils 802 and 4943 µg kg-1, respectively, with ∑3cPAHs being 6-16 times greater than ∑7cPAHs. Based on ArcGIS maps, the concentrations of ∑3cPAHs in commercial sites, business district and heavy-traffic areas were higher. The concentrations of ∑3cPAHs have not been reported, but they had significant impacts on risk assessment of urban soils due to their high relative potency factor. However, their bioaccessibility based on n-butanol extraction in soils of both cities were low, averaging 3.4-7.4%. Therefore, to accurately assess the risk of soils contaminated with PAHs, emerging cPAHs together with USEPA 7cPAHs and their bioaccessibility need to be considered.

Arsenic removal and biomass reduction of As-hyperaccumulator Pteris vittata: Coupling ethanol extraction with anaerobic digestion.

Improper disposal of arsenic-rich biomass and the lack of efficient methods to treat it may cause contamination in the environment. We developed an efficient method for arsenic (As) removal and biomass reduction of As-rich biomass of the As-hyperaccumulator Pteris vittata by coupling ethanol extraction with anaerobic digestion. This study assessed As partitioning among the three phases (gas, liquid and solid) after anaerobic digestion of P. vittata biomass. Biomass with and without As was first extracted with ethanol. Ethanol extraction removed ~93% As, with remaining As concentration at 197 mg kg-1. The extracted biomass was then digested at 35 °C under anaerobic conditions for 35 d. Arsenic in the digested biomass was reduced by 89%, with remaining As concentration at 60 mg kg-1. In addition, anaerobic digestion reduced the biomass by 64-71% and decreased the volatile solids content from 94 to 15-18%. Methane production was 145 and 160 LNCH4/kgVS after 35 d for As-rich and control biomass, respectively. As a final step, As concentration in anaerobic digestate supernatant was reduced to 0.26 mg L-1 by As-Mg precipitation. Overall, coupling ethanol extraction with anaerobic digestion decreased As concentration in P. vittata biomass from 2665 to 60 mg kg-1, or by 98%. At this level (<100 mg As kg-1), P. vittata biomass can be considered a safe material based on USEPA regulations. Effective As removal from P. vittata biomass prior to disposal improves the phytoremediation process and lowers biomass transport and landfill disposal costs.

PAHs in urban soils of two Florida cities: Background concentrations, distribution, and sources.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous organic contaminants, which are found in soils throughout the U.S. The objective of this study was to determine the background concentrations, distributions, and sources of 16 USEPA priority PAHs in two urban soils. A total of 114 soil samples were collected from two large cities in Florida: Orlando and Tampa. The results showed that soils were dominated by high molecular weight PAHs in both cities. The average ∑16-PAHs in Orlando and Tampa soils were 3227 and 4562 µg kg-1, respectively. The averages of 7 carcinogenic PAHs based on the benzo[a]pyrene-equivalent (BaP-EQ) concentrations in the two cities were 452 and 802 µg kg-1. BaP-EQ concentrations in 60-62% of samples were higher than the Florida Soil Cleanup Target Level (FSCTL) for residential soils at 100 µg kg-1 and 20-25% of samples were higher than FSCTL for industrial soils at 700 µg kg-1. Based on molecular diagnostic ratios and PMF modeling, major sources of soil PAHs in both cities were similar, mainly from pyrogenic sources including vehicle emissions, and biomass and coal combustion. Based on ArcGIS mapping, PAH concentrations in soils near business districts and high traffic roads were higher. Thus, it is important to consider background PAH concentrations in urban soils when considering soil remediation.

Arsenic removal by As-hyperaccumulator Pteris vittata from two contaminated soils: A 5-year study.

The ability of As-hyperaccumulator Pteris vittata to remove As from two contaminated soils (CCA from an As-treated wood facility and DVA from a cattle-dipping vat) over 5 years was investigated for the first time. The goal was to evaluate P. vittata's ability to continuously remove As during 10 harvests and identify how soil As was affected by P. vittata under P-sufficient (P-fertilizer) and P-limiting (phosphate rock) conditions. Sequential extraction was used to determine changes in metal distribution among different soil fractions. The high frond biomass production occurred on the 9th (62.1-63.9 and 35.6-63.5 g plant-1) and 10th harvest (58.6-60.7 and 51.9-57.1 g plant-1) for CCA and DVB soils, though frond As concentration decreased. Soil arsenic removal averaged 7-10% per harvest during the 1-6th harvests and was reduced to 0-3% during the 7-10th harvests for DVA and CCA soils. Arsenic from all fractions, excluding the residual fraction, was affected by plant uptake. The largest reduction occurred in the amorphous fraction of CCA-soil at 64-66% (61.2-61.5 to 20.8-21.8 mg kg-1) and in the crystalline fraction of DVA-soil at 50-86% (2.18-4.35 to 0.61-1.10 mg kg-1). Soil As concentrations were reduced by 37-47% from 26.7 to 129 to 15.6-16.8 and 68.9-70.1 mg kg-1 for the DVA and CCA soils, respectively. Our data indicated that P. vittata efficiently solubilized non-labile As under P-limiting conditions without impacting its As depletion.

Speciation, bioaccessibility and potential risk of chromium in Amazon forest soils.

Even though the Amazon region is widely studied, there is still a gap regarding Cr exposure and its risk to human health. The objectives of this study were to 1) determine Cr concentrations in seven chemical fractions and 6 particle sizes in Amazon soils, 2) quantify hexavalent Cr (CrVI) concentrations using an alkaline extraction, 3) determine the oral and lung bioaccessible Cr, and 4) assess Cr exposure risks based on total and bioaccessible Cr in soils. The total Cr in both A (0-20 cm) and B (80-100 cm) horizons was high at 2346 and 1864 mg kg-1. However, sequential extraction indicated that available Cr fraction was low compared to total Cr, with Cr in the residual fraction being the highest (74-76%). There was little difference in total Cr concentrations among particle sizes. Hexavalent Cr concentration was also low, averaging 0.72 and 2.05 mg kg-1 in A and B horizon. In addition, both gastrointestinal (21-22 mg kg-1) and lung (0.95-1.25 mg kg-1) bioaccessible Cr were low (<1.2%). The low bioavailability of soil Cr and its uniform distribution in different particle sizes indicated that Cr was probably of geogenic origin. Exposure based on total Cr resulted in daily intake > the oral reference dose for children, but not when using CrVI or bioaccessible Cr. The data indicated that it is important to consider both Cr speciation and bioaccessibility when evaluating risk from Cr in Amazon soils.

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.

Arsenic removal from As-hyperaccumulator Pteris vittata biomass: Coupling extraction with precipitation.

Proper disposal of As-hyperaccumulator Pteris vittata biomass (Chinese brake fern) enhances its application in phytoremediation. The goal of this study was to optimize As removal from P. vittata (PV) biomass by testing different particle sizes, extractants, extraction times and solid-to-liquid ratios. PV biomass was extracted using different extractants followed by different Mg-salts to recover soluble As via precipitation. Water-soluble As in PV biomass varied from 6.8% to 61% of total As depending on extraction time, with 99% of As being arsenate (AsV). Extraction with 2.1% HCl, 2.1% H3PO4, 1 M NaOH and 50% ethanol recovered 81, 78, 47 and 14% of As from PV biomass. A follow-up extraction using HCl recovered 27-32% with ethanol recovering only 5%. Though ethanol showed the lowest extractable As, residual As in the biomass was also the lowest. Among the extractants, 35% ethanol was the best to remove As from PV biomass. Approximately 90% As was removed from PV biomass using particle size <1 mm at solid:liquid ratio 1:50 and pH 6 for 2 h. Adding MgCl2 at As:Mg ratio of 1:400 with pH 9.5 was effective to precipitate soluble As, resulting in 98% removal. Effective removal of As from PV biomass prior to disposal helps make phytoremediation more feasible.

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.

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.