Incorporating oral, inhalation and dermal bioaccessibility into human health risk characterization following exposure to Chromated Copper Arsenate (CCA)-contaminated soils.

Exposure to potentially toxic metal(loid)s (PTMs) in soil may happen via ingestion, inhalation, and dermal pathway. A more accurate risk characterization should consider PTM bioavailability. Using ten soil samples collected in the Montreal area (Canada) near CCA-treated utility poles, this study aims to characterize non-carcinogenic and carcinogenic human health risks associated with As, Cr, Cu, Pb, and Zn through a multi-pathway exposure approach. This innovative study incorporates, for the first time, the bioaccessible fraction of the metal(loid)s for three exposure routes and two different scenarios. For the residential and industrial scenarios, the oral and dermal pathways yielded a hazard index (HI) much higher than 1 with and without bioaccessibility considerations (range 1.7 - 349 without bioaccessibility and 0.8-134 with bioaccessibility), whereas the inhalation pathway caused a lower hazard (HI < 1). For the dermal pathway, the hazard quotient was higher when bioaccessibility of field-collected samples was considered due to inherent assumptions from the US EPA soil approach to calculate the dermal dose. For carcinogenic risk, As and Pb were the most significant contributors to risk for the oral pathway, followed by the same elements for the dermal pathway. The overall carcinogenic risk was higher than the acceptable risk ( > 10-4) with and without bioaccessibility considerations (range 1.9E-4 - 9.6E-3 without bioaccessibility and 6.8E-5 - 3.8E-3 with bioaccessibility). Bioaccessibility tests provide a more accurate assessment of exposure to PTMs compared to total concentrations in soils.

Comparison of Synthetic Sweat and Influence of Sebum in the Permeation of Bioaccessible Metal(loid)s from Contaminated Soils through a Synthetic Skin Membrane.

Dermal exposure to metal(loid)s from contaminated soils has received less attention than oral and inhalation exposure. Still, it can be a relevant pathway for some contaminants. Comparison of synthetic sweats (donor solutions), the influence of sebum, and the characterization of diffusion parameters through a synthetic membrane (acting as skin surrogate) in the permeation of metal(loid)s (As, Cr, Cu, Ni, Pb, and, Zn) from polluted soils is missing. The dermal bioaccessibility tests were performed using two sweat compositions [EN 1811, pH 6.5 (sweat A) and NIHS 96-10, pH 4.7 (sweat B)]. Diffusion parameters of soluble metal(loid)s using the Franz cell methodology were calculated using the Strat-M membrane. The influence of synthetic sebum in the permeation of metal(loid)s was also investigated. The metal(loid) bioaccessibility percentage was higher for sweat B (pH 4.7) compared to sweat A (pH 6.5), attributed to lower pH of sweat B. Among the six elements tested, only chromium and copper permeated the membrane. Permeation coefficient (Kp) was higher for chromium in sweat A (0.05-0.11 cm h-1) than sweat B (0.0007-0.0037 cm h-1) likely due to a higher pH and thus more permeable Cr species. The presence of sebum increased lag times for copper permeation. Additional studies regarding speciation of metal(loid)s following extractions in synthetic sweat and comparison of synthetic membrane Strat-M and human skin in the permeation of metal(loid)s are recommended.

Metals and metalloids treatment in contaminated neutral effluents using modified materials.

Circumneutral surface water and groundwater can contain hazardous concentrations of metals and metalloids that can threaten organisms in surrounding ecosystems. Extensive research has been conducted over the past two decades to prevent, limit, and treat water pollution. Among the currently available treatment options is the use of natural and residual materials, which is generally regarded as effective and inexpensive. The modification of such materials enhances the removal capacity of metals and metalloids, as well as the physical and chemical stability of the materials and resulting sludge (after treatment). This paper reviews several modified materials that have produced and evaluated in the past twenty years to treat various contaminants in water under specific conditions. Important factors on performance improvement following the modifications are emphasized. Sorption capacity and kinetics, and element removal mechanisms are also discussed. Element recovery, material regeneration, water reuse, evaluation of treatment efficiency for real effluents are also considered, as well as the applicability of these materials in both active and passive treatment systems. Modified natural and residual materials are a promising option for the treatment of metals and metalloids in circumneutral contaminated waters. However, further research is necessary to evaluate their field-scale performance and to properly assess treatment costs.

Iron removal in highly contaminated acid mine drainage using passive biochemical reactors.

Passive biochemical reactors (PBRs) are a viable alternative to neutralization plants for the treatment of acid mine drainage (AMD) because they require lower investment costs and use residual materials. However, high iron (Fe) concentrations (≥0.5 g/L) in AMD are challenging for their long-term efficiency. Sorption and precipitation are the main Fe removal mechanisms, but the relative importance of each is mostly unknown. In this study, locally available natural materials (organic and inorganic) were characterized and tested for their performance in Fe removal from highly contaminated AMD (pH 3.5, 4 g/L of Fe, and 9 g/L of sulfate). Iron retention capacity of the materials was then evaluated and the efficiency of eight mixtures of materials was compared through 40-day laboratory batch tests. All batch-type PBRs increased the pH up to 6.5 and decreased dissolved metals concentrations, including Fe, up to 99%. Results showed that organic residual materials (manures, municipal wastewater sludge, and compost) were the best substrates for Fe removal.These findings allowed for the selection of three reactive mixtures with distinct characteristics (mixture #1 - 30% organic wastes; mixture #4 - 50% calcite; and mixture #7 - 50% sand) to be further evaluated in column type PBRs.

Valorization of a treated soil via amendments: fractionation and oral bioaccessibility of Cu, Ni, Pb, and Zn.

The present study aims to transform a treated soil (TS) into a more desirable resource by modifying physico-chemical properties via amendments while reducing toxic metals' mobility and oral bioaccessibility. A hydrocarbon-contaminated soil submitted to treatment (TS) but still containing elevated concentrations of Cu, Ni, Pb, and Zn has been amended with compost, sand, and Al2(SO4)3 to render it usable for horticulture. Characterization and sequential extraction were performed for TS and four amended mixtures (AM1-4). P and K availability and metal bioaccessibility were investigated in TS and AM2. Amendment improved soil properties for all mixtures and yielded a usable product (AM2 20 % TS, 49 % compost, 30 % sand, 1 % Al2(SO4)3) satisfying regulatory requirements except for Pb content. In particular, AM2 had improved organic matter (OM) and cation exchange capacity (CEC), highly increased P and K availability, and reduced total metal concentrations. Furthermore, amendment decreased metal mobile fraction likely to be plant-available (in mg kg(-1), assumed as soluble/exchangeable + carbonates fractions). For AM2, estimated Pb bioavailability decreased from 1.50 × 10(3) mg kg(-1) (TS) to 238 mg kg(-1) (52.4 % (TS) to 34.2 %). Bioaccessible concentrations of Cu, Ni, and Zn (mg kg(-1)) were lower in AM2 than in TS, but there was no significant decrease for Pb. The results suggest that amendment improved soil by modifying its chemistry, resulting in lower metal mobile fraction (in %, for Cu and Zn) and bioaccessibility (in %, for Cu only). Amending soils having residual metal contamination can be an efficient valorization method, indicating potential for reducing treatment cost and environmental burden by rendering disposal/additional treatment unnecessary. Further studies including plant bioavailability are recommended to confirm results.

Bioaccessibility of As, Cd, Cu, Ni, Pb, and Sb in toys and low-cost jewelry.

Children can be exposed to toxic elements in toys and jewelry following ingestion. As, Cd, Cu, Ni, Pb, and Sb bioavailability was assessed (n = 24) via the in vitro gastrointestinal protocol (IVG), the physiologically based extraction test (PBET), and the European Toy Safety Standard protocol (EN 71-3), and health risks were characterized. Cd, Cu, Ni, and Pb were mobilized from 19 metallic toys and jewelry (MJ) and one crayon set. Bioaccessible Cd, Ni, or Pb exceeded EU migratable concentration limits in four to six MJ, depending on the protocol. Using two-phase (gastric + intestinal) IVG or PBET might be preferable over EN 71-3 since they better represent gastrointestinal physiology. Bioaccessible and total metal concentrations were different and not always correlated, indicating that bioaccessibility measurement may provide more accurate risk characterization. More information on impacts of multiple factors affecting metals mobilization from toys and jewelry is needed before recommending specific tests. Hazard index (HI) for Cd, Ni, or Pb were >1 for all six MJ exceeding the EU limits. For infants (6-12 mo old), 10 MJ had HI > 1 for Cd, Cu, Ni, or Pb (up to 75 for Cd and 43 for Pb). Research on prolonged exposure to MJ and comprehensive risk characterization for toys and jewelry exposure is recommended.

Estimating children's exposure to toxic elements in contaminated toys and children's jewelry via saliva mobilization.

Children's potential for exposure to potentially toxic elements in contaminated jewelry and toys via mouth contact has not yet been fully evaluated. Various toys and jewelry (metallic toys and jewelry [MJ], plastic toys, toys with paint or coating, and brittle/pliable toys; n = 32) were tested using the saliva extraction (mouthing) compartment of the DIN and RIVM bioaccessibility protocols to assess As, Ba, Cd, Cr, Cu, Mn, Ni, Pb, Sb, and Se mobilization via saliva. Total concentrations of As, Cd, Cu, Ni, Pb, and Sb were found elevated in analyzed samples. Four metals were mobilized to saliva from 16 MJ in significant quantities (>1 µg for highly toxic Cd and Pb, >10 µg for Cu and Ni). Bioaccessible concentrations and hazard index values for Cd exceeded limit values, for young children between 6 mo- and 3 yr-old and according to both protocols. Total and bioaccessible metal concentrations were different and not always correlated, encouraging the use of bioaccessibility for more accurate hazard assessments. Bioaccessibility increased with increasing extraction time. Overall, the risk from exposure to toxic elements via mouthing was high only for Cd and for MJ. Further research on children's exposure to toxic elements following ingestion of toy or jewelry material is recommended.

Contamination by ten harmful elements in toys and children's jewelry bought on the North American market.

Toys and children's jewelry may contain metals to which children can be orally exposed. The objectives of this research were (1) to determine total concentrations (TC's) of As, Ba, Cd, Cr, Cu, Mn, Ni, Pb, Sb, and Se in toys and jewelry (n = 72) bought on the North American market and compare TC's to regulatory limits, and (2) to estimate oral metal bioavailability in selected items (n = 4) via bioaccessibility testing. For metallic toys and children's jewelry (n = 24) 20 items had TC's exceeding migratable concentration limits (European Union). Seven of seventeen jewelry items did not comply with TC limits in U.S. and Canadian regulations. Samples included articles with very high Cd (37% [w/w]), Pb (65%), and Cu (71%) concentrations. For plastic toys (n = 18), toys with paint or coating (n = 12), and brittle or pliable toys (n = 18), TC's were below the EU migration limits (except in one toy for each category). Bioaccessibility tests showed that a tested jewelry item strongly leached Pb (gastric: 698 µg, intestinal: 705 µg) and some Cd (1.38 and 1.42 µg). Especially in metallic toys and jewelry, contamination by Pb and Cd, and to a lesser extent by Cu, Ni, As, and Sb, still poses an acute problem in North America.

Simultaneous removal of nitrate and sulfate from greenhouse wastewater by constructed wetlands.

This study evaluated the effectiveness of C-enriched subsurface-flow constructed wetlands in reducing high concentrations of nitrate (NO) and sulfate (SO) in greenhouse wastewaters. Constructed wetlands were filled with pozzolana, planted with common cattail (), and supplemented as follows: (i) constructed wetland with sucrose (CW+S), wetland units with 2 g L of sucrose solution from week 1 to 28; (ii) constructed wetland with compost (CW+C), wetland units supplemented with a reactive mixture of compost and sawdust; (iii) constructed wetland with compost and no sucrose (CW+CNS) from week 1 to 18, and constructed wetland with compost and sucrose (CW+CS) at 2 g L from week 19 to 28; and (iv) constructed wetland (CW). During 28 wk, the wetlands received a typical reconstituted greenhouse wastewater containing 500 mg L SO and 300 mg L NO. In CW+S, CW+C, and CW+CS, appropriate C:N ratio (7:3.4) and redox potential (-53 to 39 mV) for denitrification resulted in 95 to 99% NO removal. Carbon source was not a limiting factor for denitrification in C-enriched constructed wetlands. In CW+S and CW+CS, the dissolved organic carbon (DOC)/SO ratios of 0.36 and 0.28 resulted in high sulfate-reducing bacteria (SRB) counts and high SO removal (98%), whereas low activities were observed at DOC/SO ratios of 0.02 (CW) to 0.11 (CW+C, CW+CNS). On week 19, when organic C content was increased by sucrose addition in CW+CS, SRB counts increased from 2.80 to 5.11 log[CFU+1] mL, resulting in a level similar to the one measured in CW+S (4.69 log[CFU+1] mL). Consequently, high sulfate reduction occurred after denitrification, suggesting that low DOC (38-54 mg L) was the limiting factor. In CW, DOC concentration (9-10 mg L) was too low to sustain efficient denitrification and, therefore, sulfate reduction. Furthermore, the high concentration of dissolved sulfides observed in CW+S and CW+CS treated waters were eliminated by adding FeCl.

Children's exposure to mercury-contaminated soils: exposure assessment and risk characterization.

Exposure to mercury (Hg)-contaminated soils may pose a health risk to children by way of oral, dermal, and inhalatory pathways. However, risk characterization studies, including contaminant bioaccessibility with child-specific exposure parameters and scenarios, are lacking. The objectives of this study were (1) to assess children's Hg exposure using characterization and oral bioaccessibility data from Hg-contaminated soils characterized in previous studies (n = 8); and (2) to characterize probabilistic risk in terms of hazard index (HI) considering ingestion, dermal, and inhalation pathways. Total Hg concentrations in soils ranged from 2.61 to 1.15 × 10(4) mg kg(-1). For moderately contaminated soils (S1-S5: Hg ≤ 12.15 mg kg(-1)), low oral bioaccessibility values (1.5-7.5 %) lead to HI < 1 in all scenarios. However, exposure to highly contaminated soils (S6-S8) may pose serious risks to children under normal exposure (HI 0.89-66.5) and soil-pica behaviour scenarios (HI up to 131). All three pathways significantly contributed to the risk. Using total Hg concentrations in calculations (assuming 100 % bioavailability) instead of considering Hg bioavailability leads to risk overestimation. Further research on oral, inhalatory, and dermal bioavailability of Hg, as well as child play behaviour, is recommended to obtain more accurate risk estimates.

Use of a passive bioreactor to reduce water-borne plant pathogens, nitrate, and sulfate in greenhouse effluent.

The goal of this study was to evaluate the use of passive bioreactors to reduce water-borne plant pathogens (Pythium ultimum and Fusarium oxysporum) and nutrient load (NO(-) 3 and SO(2-) 4) in greenhouse effluent. Sterilized and unsterilized passive bioreactors filled with a reactive mixture of organic carbon material were used in three replicates. After a startup period of 2 (sterilized) or 5 (unsterilized) weeks, the bioreactor units received for 14 weeks a reconstituted commercial greenhouse effluent composed of 500 mg L(-1) SO(2-) 4 and 300 mg L(-1) NO(-) 3 and were inoculated three times with P. ultimum and F. oxysporum (10(6) CFU mL(-1)). Efficacy in removing water-borne plant pathogens and nitrate reached 99.9% for both the sterilized and unsterilized bioreactors. However, efficacy in reducing the SO(2-) 4 load sharply decreased from 89% to 29% after 2 weeks of NO(-) 3-supply treatment for the unsterilized bioreactors. Although SO(2-) 4 removal efficacy for the sterilized bioreactors did not recover after 4 weeks of NO(-) 3-supply treatment, the unsterilized bioreactor nearly reached a similar level of SO(2-) 4 removal after 4 weeks of NO(-) 3-supply treatment compared with affluent loaded only with SO(2-) 4, where no competition for the carbohydrate source occurred between the denitrification process and sulfate-reducing bacteria activity. Performance differences between the sterilized and unsterilized bioreactors clearly show the predominant importance of sulfate-reducing bacteria. Consequently, when sulfate-reducing bacteria reach their optimal activity, passive bioreactors may constitute a cheap, low-maintenance method of treating greenhouse effluent to recycle wastewater and eliminate nutrient runoff, which has important environmental impacts.

Variability of bioaccessibility results using seventeen different methods on a standard reference material, NIST 2710.

Bioaccessibility is a measurement of a substance's solubility in the human gastro-intestinal system, and is often used in the risk assessment of soils. The present study was designed to determine the variability among laboratories using different methods to measure the bioaccessibility of 24 inorganic contaminants in one standardized soil sample, the standard reference material NIST 2710. Fourteen laboratories used a total of 17 bioaccessibility extraction methods. The variability between methods was assessed by calculating the reproducibility relative standard deviations (RSDs), where reproducibility is the sum of within-laboratory and between-laboratory variability. Whereas within-laboratory repeatability was usually better than (<) 15% for most elements, reproducibility RSDs were much higher, indicating more variability, although for many elements they were comparable to typical uncertainties (e.g., 30% in commercial laboratories). For five trace elements of interest, reproducibility RSDs were: arsenic (As), 22-44%; cadmium (Cd), 11-41%; Cu, 15-30%; lead (Pb), 45-83%; and Zn, 18-56%. Only one method variable, pH, was found to correlate significantly with bioaccessibility for aluminum (Al), Cd, copper (Cu), manganese (Mn), Pb and zinc (Zn) but other method variables could not be examined systematically because of the study design. When bioaccessibility results were directly compared with bioavailability results for As (swine and mouse) and Pb (swine), four methods returned results within uncertainty ranges for both elements: two that were defined as simpler (gastric phase only, limited chemicals) and two were more complex (gastric + intestinal phases, with a mixture of chemicals).

Influence of sebum proportion in synthetic sweat on dermal bioaccessibility and on permeation of metal(loid)s from contaminated soils.

Even if dermal exposure to metal(loid)s from contaminated soils has received less attention than oral and inhalation exposure, the human health risk can be significant for some contaminants and exposure scenarios. The purpose of this study was to assess the influence of sebum proportion (1% v/v and 3% v/v) in two synthetic sweat formulations (EN 1811, pH 6.5 (sweat A) and NIHS 96-10, pH 4.7 (sweat B)) on As, Cr, Cu, Ni, Pb, and Zn dermal bioaccessibility and on subsequent diffusion through synthetic skin. A Franz cell with a Strat-M® membrane was used to quantify permeation parameters of bioaccessible metal(loid)s. Sebum's presence in synthetic sweat formulations significantly modified bioaccessibility percentages for As, Cr, and Cu. However, sebum proportion in both sweats did not influence the bioaccessibility of Pb and Zn. Some metal(loid)s, namely As and Cu, permeated the synthetic skin membrane during permeation tests when sebum was added to sweat while no permeation was observed without sebum in sweat formulations. Depending on sweat formulation, the addition of sebum (1% v/v) increased or decreased the Cr permeation coefficients (Kp). In all cases, bioaccessible Cr was no longer permeable when extracted with 3% sebum. Ni transdermal permeation was not influenced by the presence of sebum, and no permeation was observed for Pb and Zn. Further studies on the speciation of metal(loid)s in bioaccessible extracts in the presence of sebum are recommended.

Occurrence of metals in e-cigarette liquids: Influence of coils on metal leaching and exposure assessment.

Electronic cigarettes are generally recognized as a safer alternative than conventional cigarettes. Nevertheless, previous research suggests metal (loid) leaching due to coil contact, potentially transferring to the e-liquid and its aerosolized form. In this study, Cr, Cd, Ni, and Pb levels were measured by inductively coupled plasma mass spectrometry (ICP-MS) on 17 samples of e-liquids with different chemical properties (e.g., pH, nicotine content, flavoring, free-base, and nicotine salts). Twelve e-liquids were then put in contact with 36-gauge Kanthal A-1, Nichrome 80, Stainless steel 317 L and disposable coils such as Juul, and Aspire BVC for three days at 200-250 °C for 1 h each day. Metal levels expressed as mean (standard deviation) metal concentration, were below detection (Cd) to very low in bottle samples (Ni ≤ 76 (18); Pb ≤ 16 (1.5); and Cr ≤ 386 (15.6) µg/kg). In the coil extracts, varying concentrations of the same metal (loid) were found, indicating that metal leaching capacity may differ per sample. All samples contained Ni and Cr, followed by Pb to a much lesser extent. Cd levels were mostly below detection limits. Coil + e-liquid combinations with the highest Ni, Cr, and Pb concentrations were: Aspire BVC + Melon 0 mg/mL: Ni = 1.22 E+04 (281); Aspire BVC + Hit Nicotine 40 mg/mL: Cr = 864 (116); and Nichrome 80 + Melon 0 mg/mL: Pb = 56 (5) µg/kg. Overall, results suggest that nicotine salts at 40 mg/mL enhance Cr and Ni transfer. Stainless steel 317 L released very low metal concentrations. A conservative screening level risk characterization showed that 10.5% and 3.5% of the coil extracts may exceed Ni and Cr (III) safe concentrations, respectively. In the aerosol phase, 8.8% of samples might be above Ni equivalent daily dose for chronic exposure and 1.8% for intermediate exposure. Further studies on coil metal leaching could aid in establishing coil manufacturing regulations.

Metal(loid) speciation in dermal bioaccessibility extracts from contaminated soils and permeation through synthetic skin.

Dermal exposure to metal(loid)s from contaminated soils can contribute to health risk. Metal(loid) speciation will influence their bioaccessibility in sweat and subsequent permeation across the skin. Therefore, the speciation of the bioaccessible fraction of metal(loid)s in two synthetic sweat formulations (sweat A (pH 6.5) and B (pH 4.7)) was assessed using chemical equilibrium modelling (Visual MINTEQ). Permeation through synthetic skin and the influence of sebum in the permeation of As, Cr, Cu, Ni, Pb, and Zn were also investigated using Franz cells. Following dermal bioaccessibility tests for five Chromated Copper Arsenate (CCA)-contaminated soils and one certified soil (SQC001), mean metal(loid) bioaccessibility (%) was higher in sweat B (2.33-18.8) compared to sweat A (0.12-7.53). Arsenic was almost entirely found as As(V) in both sweats. In sweat A, comparable concentrations of Cr(III) and Cr(VI) were found whereas in sweat B, Cr was primarily present as Cr(III). Copper was primarily found as Cu2+. Bioaccessible Cr extracted from nearly all soils permeated through the Strat-M membrane when it was coated with sebum. The Cr permeation coefficient (Kp) ranged between 0.004 and 0.13 cm/h and the Kp for Cu was higher (0.024-0.52 cm/h). As, Ni, Pb, and Zn did not permeate the synthetic skin.

Heavy metals in toys and low-cost jewelry: critical review of U.S. and Canadian legislations and recommendations for testing.

High metal contamination in toys and low-cost jewelry is a widespread problem, and metals can become bioavailable, especially via oral pathway due to common child-specific behaviors of mouthing and pica. In this review, the U.S., Canadian, and European Union (EU) legislations on metals in toys and jewelry are evaluated. A literature review on content, bioavailability, children's exposure, and testing of metals in toys and low-cost jewelry is provided. A list of priority metals is presented, and research needs and legislative recommendations are addressed. While the U.S. and Canadian legislations put emphasis on lead exposure prevention, other toxic elements like arsenic and cadmium in toy materials are not regulated except in paint and coatings. The EU legislation is more comprehensive in terms of contaminants and scientific approach. Current toy testing procedures do not fully consider metal bioavailability. In vitro bioaccessibility tests developed and validated for toys and corresponding metal bioaccessibility data in different toy matrices are lacking. The U.S. and Canadian legislations should put more emphasis on metal bioavailability and on other metals in addition to lead. A two-step management approach with mandatory testing of toys for total metal concentrations followed by voluntary bioaccessibility testing could be implemented.

Using fluorescence-based microplate assay to assess DOM-metal binding in reactive materials for treatment of acid mine drainage.

One potential drawback of compost-based passive bioreactors, which is a promising biotechnology for acid mine drainage (AMD) treatment, is the transport of dissolved organic matter (DOM)-metal complexes in surface waters. To address this problem, the objective of this study was to assess the maximum capacity of organic substrates to release soluble DOM-metal complexes in treated water. The reactivities of DOM in maple wood chips and sawdust, composted poultry manure, and leaf compost were quantified toward Cd2+, Ni2+, Fe2+, and Cu2+ using fluorescence quenching. The DOM showed the highest reactivity toward Fe, but a limited number of available sites for sorption, whereas DOM-Cd complexes exhibited the lowest fluorescence quenching. Overall, the DOM from a mixture of wastes formed higher concentrations of DOM-metal complexes relative to sole substrates. Among DOM-metal complexes, the concentrations of DOM-Ni complexes were the highest. After reaching steady-state, low concentrations of DOM-metal complexes were released in treated water, which is in agreement with theoretical predictions based on geochemical modeling. Therefore, in addition to physicochemical characterization, fluorescence quenching technique is recommended for the substrate selection of bioreactors.

Removal of nickel from neutral mine drainage using peat-calcite, compost, and wood ash in column reactors.

The effectiveness of compost, peat-calcite, and wood ash to remove Ni from a circum-neutral-contaminated mine water was tested in continuous flow experiments. Materials were compared in 4.8-L columns at hydraulic residence times (HRT) of ∼ 16.5 h over the course of 2.5-4 months. During this period, all columns successfully treated over 400 L of synthetic contaminated neutral drainage (4.05 mg/L Ni), mainly through sorption processes. Mid-column results (HRT ∼ 9 h) indicated that wood ash was the most effective material for Ni removal, and chemical extractions revealed that retained Ni was less mobile in this spent material. The pH-increasing properties of wood ash played a major role in this material's performance, but a pH correction would be required in the initial stages of full-scale treatment to maintain the effluent within regulatory limits (6-9.5). Scaled to full-sized, mid-column results indicated that treatment cell sizes, designed for the 1-year treatment of a high discharge (10 m3/h)-contaminated effluent (4.05 mg/L Ni), would be the smallest with wood ash (< 500 m3), followed by compost (600 ± 140 m3) and peat-calcite (720 ± 50 m3).

Metal(loid)s inhalation bioaccessibility and oxidative potential of particulate matter from chromated copper arsenate (CCA)-contaminated soils.

Field-collected chromated copper arsenate (CCA)-contaminated soils and associated particulate matter (PM) were characterized for their total metal(loid)s content (As, Cr, Cu, Fe, Mn, Ni, Pb and Zn) and physicochemical properties. Copper, Ni, Pb and Zn fractionation (using sequential extraction) and inhalation bioaccessibility (using two lung fluids) of trace elements were assessed in PM samples. In Gamble's solution (GS), low average bioaccessibility (up to 12%) was observed for As, Cu, Mn, and Ni. A strong correlation (r = 0.92, p < 0.005, n = 9) between the soluble and exchangeable fraction (F1) and bioaccessibility in GS was observed for Cu. Inhalation bioaccessibility in artificial lysosomal fluid (ALF) was higher for Cu (avg. 78.5 ± 4.2%), Mn (avg. 56.8 ± 12.1%), Zn (avg. 54.8 ± 24.5%) and As (avg. 45.4 ± 18.8%). Strong correlations between inhalation bioaccessibility in ALF and the mobile (i.e. F1+F2) metal fraction were observed for all tested metals (i.e. (Cu (r = 0.95, p < 0.005), Ni (r = 0.79, p < 0.05), Pb (r = 0.92, p < 0.005) and Zn (r = 0.98, p < 0.005)), n = 9). The oxidative potential (OP) of PM was also assessed using an ascorbate (AA) depletion assay (OPAA). Mobile Cu fractions were deemed to be the main factor influencing OPAA ((F1 (r = 0.99, p < 0.005), F2 (r = 0.97, p < 0.005)), n = 9) in PM samples. A strong correlation (r = 0.94, p < 0.005, n = 10) was also observed between Cu bioaccessibility in GS and OPAA.

Oral and inhalation bioaccessibility of metal(loid)s in chromated copper arsenate (CCA)-contaminated soils: Assessment of particle size influence.

Soil samples adjacent to ten CCA-treated utility poles were collected, sieved into four fractions (<2 mm, 250-90 µm, 90-20 µm and <20 µm), and characterized for their total metal(loid) (As, Cu, Cr, Pb, and Zn) content and physico-chemical properties. Oral bioaccessibility tests were performed using In Vitro Gastrointestinal (IVG) method for fractions 250-90 µm and 90-20 µm. Inhalation bioaccessibility tests were performed in particle size fraction <20 µm using two simulated lung fluids: artificial lysosomal fluid (ALF) and Gamble's solution (GS). The total concentration of metal(loid)s increased with decreasing particle size. Oral As bioaccessibility (%) increased with increasing particle size in 9 out of 10 soils (p < .05), but oral As bioaccessibility expressed in mg/kg was not significantly different for both particle size. Oral Cu bioaccessibility (% and mg/kg) was not influenced by particle size, but oral Cr bioaccessibility (% and mg/kg) increased when reducing particle size (p < .05), although Cr bioaccessibility was very low (< 8%). Oral bioaccessibility (%) of metal(loid)s decreased in the order: Cu > As > Pb > Zn > Cr. Bioaccessibility (%) in simulated lung fluids decreased in the order: Cu > Zn > As > Pb ≈ Cr using ALF, and As > Cu using GS solution. For all elements, inhalation bioaccessibility (% and mg/kg) using ALF was higher than oral bioaccessibility, except for Pb bioaccessibility (mg/kg) in two samples. However, solubility of metal(loid)s in GS presented the lowest values. Copper showed the highest oral and inhalation bioaccessibility (%) and Cr showed the lowest. Moreover, organic matter content and cation exchange capacity in particle size 90-20 µm were negatively correlated with Cu and Pb oral bioaccessibility (%).