Online sorting of recovered wood waste by automated XRF-technology. Part I: detection of preservative-treated wood waste

Waste wood is frequently contaminated with wood treatment preservatives including chromated copper arsenate (CCA) and alkaline copper quat (ACQ), both of which contain metals which contaminate recycled wood products. The objective of this research was to propose a design for online automated identification of As-based and Cu-based treated wood within the recovered wood waste stream utilizing an X-ray fluorescence (XRF) system, and to evaluate the detection parameters of such system. A full-scale detection unit was used for experimentation. Two main parameters (operational threshold (OT) and measurement time) were evaluated to optimize detection efficiencies. OTs of targeted metals, As and Cu, in wood were reduced to 0.02 and 0.05, respectively. The optimum minimum measurement time of 500 ms resulted in 98%, 91%, and 97% diversion of the As, Cu and Cr mass originally contained in wood, respectively. Comparisons with other detection methods show that XRF technology can potentially fulfill the need for cost-effective processing at large facilities (>30 tons per day) which require the removal of As-based preservatives from their wood waste stream.     

Factors affecting sodium hypochlorite extraction of CCA from treated wood

Significant amounts of chromated copper arsenate (CCA) treated wood products, such as utility poles and residential construction wood, remain in service. There is increasing public concern about environmental contamination from CCA-treated wood when it is removed from service for reuse or recycling, placed in landfills or burned in commercial incinerators. In this paper, we investigated the effects of time, temperature and sodium hypochlorite concentration on chromium oxidation and extraction of chromated copper arsenate from CCA-treated wood (Type C) removed from service. Of the conditions evaluated, reaction of milled wood with sodium hypochlorite for one hour at room temperature followed by heating at 75 °C for two hours gave the highest extraction efficiency. An average of 95% Cr, 99% Cu and 96% As could be removed from CCA-treated, milled wood by this process. Most of the extracted chromium was oxidized to the hexavalent state and could therefore be recycled in a CCA treating solution. Sodium hypochlorite extracting solutions could be reused several times to extract CCA components from additional treated wood samples.     

Improving the two-step remediation process for CCA-treated wood: Part I. Evaluating oxalic acid extraction

In this study, three possible improvements to a remediation process for chromated-copper-arsenate- (CCA) treated wood were evaluated. The process involves two steps: oxalic acid extraction of wood fiber followed by bacterial culture with Bacillus licheniformis CC01. The three potential improvements to the oxalic acid extraction step were (1) reusing oxalic acid for multiple extractions, (2) varying the ratio of oxalic acid to wood, and (3) using a noncommercial source of oxalic acid such as Aspergillus niger, which produces oxalic acid as a metabolic byproduct. Reusing oxalic acid for multiple extractions removed significant amounts of copper, chromium, and arsenic. Increasing the ratio of wood to acid caused a steady decline in metal removal. Aspergillus niger removed moderate amounts of copper, chromium, and arsenic from CCA-treated wood. Although A. niger was effective, culture medium costs are likely to offset any benefits. Repeated extraction with commercial oxalic acid appears to be the most cost-effective method tested for the two-step process.     

Method to recover and reuse chromated copper arsenate wood preservative from spent treated wood

The volume of chromated copper arsenate (CCA) treated wood products coming out of service is expected to increase dramatically during the next decade. There is a need for an alternative waste management approach to landfilling. This paper investigates the variables affecting extraction of CCA components from wood particles and the potential to oxidize and reuse the recovered chemicals. Most of the CCA components could be extracted by 10% H2O2 at 50 degrees C in 6 h with an average extraction efficiency of 95% for Cr, 94% for Cu and 98% for As. The extract containing Cr(III), Cu(II) and As(V) could be oxidized in several stages by aqueous 2.5% w/w H2O2 in less than 2 h to a condition where it was compatible with CCA treating solutions and could be reused for treating new wood. When the recovered extract was mixed with fresh CCA solution in different ratios, the mixed CCA-C solutions had similar solution stability as freshly prepared CCA-C solution and treated wood had similar leaching properties as wood treated with fresh solution.     

Online sorting of recovered wood waste by automated XRF-technology: part II. Sorting efficiencies

Sorting of waste wood is an important process practiced at recycling facilities in order to detect and divert contaminants from recycled wood products. Contaminants of concern include arsenic, chromium and copper found in chemically preserved wood. The objective of this research was to evaluate the sorting efficiencies of both treated and untreated parts of the wood waste stream, and metal (As, Cr and Cu) mass recoveries by the use of automated X-ray fluorescence (XRF) systems. A full-scale system was used for experimentation. This unit consisted of an XRF-detection chamber mounted on the top of a conveyor and a pneumatic slide-way diverter which sorted wood into presumed treated and presumed untreated piles. A randomized block design was used to evaluate the operational conveyance parameters of the system, including wood feed rate and conveyor belt speed. Results indicated that online sorting efficiencies of waste wood by XRF technology were high based on number and weight of pieces (70-87% and 75-92% for treated wood and 66-97% and 68-96% for untreated wood, respectively). These sorting efficiencies achieved mass recovery for metals of 81-99% for As, 75-95% for Cu and 82-99% of Cr. The incorrect sorting of wood was attributed almost equally to deficiencies in the detection and conveyance/diversion systems. Even with its deficiencies, the system was capable of producing a recyclable portion that met residential soil quality levels established for Florida, for an infeed that contained 5% of treated wood.     

Conversion of CCA-treated wood to ethanol: a method to reduce leaching of metals from disposed treated wood prior to disposal

The objective of this paper is to evaluate the feasibility of producing ethanol from CCA-treated wood that is highly leachable. Following the initial tests, CCA-treated wood was hydrolysed and fermented and the results showed not only that ethanol was produced during the fermentation process but that metals were taken up by the yeast. Toxicity characteristic leaching procedure tests of the hydrolysed wood leached less than 4 mg/L of As while minimal amounts of Cr and Cu remained in the hydrolysed wood which makes landfilling of hydrolysed wood acceptable and less hazardous. A slightly lower amount of ethanol from CCA-treated than untreated wood was produced (6 and 7 g/L, respectively). In general, it suggests that production of ethanol as a source of energy from a hazardous waste (CCA-treated wood) is feasible.     

Improving the two-step remediation process for CCA-treated wood: Part II. Evaluating bacterial nutrient sources

Remediation processes for recovery and reuse of chromated-copper-arsenate- (CCA) treated wood are not gaining wide acceptance because they are more expensive than landfill disposal. One reason is the high cost of the nutrient medium used to culture the metal-tolerant bacterium, Bacillus licheniformis, which removes 70-100% of the copper, chromium, and arsenic from CCA-treated southern yellow pine (CCA-SYP) in a two-step process involving oxalic acid extraction and bacterial culture. To reduce this cost, the nutrient concentration in the culture medium and the ratio of wood to nutrient medium were optimized. Maximum metal removal occurred when B. licheniformis was cultured in 1.0% nutrient medium and at a wood to nutrient medium ratio of 1:10. Also, malted barley, an abundant by-product of brewing, was evaluated as an alternative nutrient medium. Tests were done to determine absorption of metals by barley, and the results indicate that the barley acted as a biosorbent, removing heavy metals from the liquid culture after their release from CCA to SYP. For comparison, tests were also performed with no nutrient medium. Following bacterial remediation, 17% copper and 15% arsenic were removed from an aqueous slurry of CCA-SYP (no medium). When oxalic acid extraction preceded the aqueous bacterial culture, 21% copper, 54% chromium, and 63% arsenic were removed. The two-step process (oxalic acid extraction and bacterial culture with nutrient medium) appears to be an effective, yet costly, way to remove metals.     

Designing a purification process for chromium-, copper- and arsenic-contaminated wood

The disposal of chromated copper arsenate (CCA)-treated wood is becoming a serious problem in many countries due to increasing levels of contamination by the hazardous elements, chromium, copper and arsenic. The present experiment was conducted as a preliminary step toward one-step solvent extraction of CCA-treated wood. Because chromium, copper and arsenic have different chemical characteristics, it is best to consider them separately prior to designing a one-step extraction process. As a basis, various two-step extraction processes were first designed and tested experimentally to determine feasibility. Among these combinations, the treatment combining oxalic acid as the 1st step and a sodium oxalate solution under acidic conditions (pH 3.2) as the 2nd step was found to be an effective way of extracting CCA elements from treated wood. Extraction efficiency reached 100% for arsenic and chromium and 95.8% for copper after a 3-h sodium oxalate treatment, following a 1-h pre-extraction process with oxalic acid. On the other hand, the same combination under alkaline conditions (pH 11.2) during the 2nd step was ineffective for copper removal, indicating that pH plays an important role in complexation with sodium oxalate solution. The present results suggest that the extraction of CCA elements using a combination of oxalic acid and acidic sodium oxalate solution is a promising basis for application to a one-step extraction method.     

Treatment of urban stormwater for dissolved pollutants: A comparative study of natural organic filter media

Sorption capacities were evaluated for the dissolved stormwater (SW) pollutants onto two tree mulches and jute fiber. SW spiked with predetermined concentrations of copper (Cu), cadmium (Cd), hexavalent chromium (Cr ⁺⁶), lead (Pb), zinc (Zn), and benzo[a]pyrene (B[a]P), naphthalene (NP), fluoranthene (FA), 1,3‐dichlorobenzene (DCB), and butylbenzylphthalate (BBP) were used in this study. Each medium removed close to 100 percent of all the pollutants at the concentrations studied. Sorption capacities (μg/g) of the three organic media were in the order of jute > hardwood mulch > softwood mulch, and on a mole basis, both the heavy metals and the toxic organics were sorbed by the three media in an identical sequence: Cr ⁺⁶ > Cu, Zn > Cd > Pb; and NP > DCB > FA > B[a]P > BBP. Sorption capacities of the hardwood wood mulch and jute fiber for the pollutants were correlated with distinctive physical properties of the pollutants. © 2005 Wiley Periodicals, Inc.     

Removal of copper,chromium, and arsenic from CCA-C treated wood by EDTA extraction

Ethylenediaminetetracetic acid (EDTA) is one of the most common chelators used to bind the metal ions in extremely stable complexes in heavy metal contaminated soils and thus to remediate such substrates. EDTA forms water soluble complexes with many metal ions and it is used to release the various metals. In this study, EDTA extraction of copper, chromium, and arsenic from chromated copper arsenate (CCA-C) treated wood was evaluated using batch leaching experiments. CCA-treated wood samples were extracted with eight different concentrations of EDTA for 4, 8, 18, and 24 h at room temperature. Exposing CCA-treated chips and sawdust to EDTA extraction enhanced removal of CCA components compared with extraction by deionized water. Grinding CCA-treated wood chips into 40-mesh sawdust provided greater access to and removal of CCA components. Extraction with 1% EDTA solution for 24 h removed 60% copper, 13% chromium, and 25% arsenic from treated chips. EDTA extraction of treated sawdust samples resulted in 93% copper, 36% chromium, and 38% arsenic removal. CCA leaching from treated wood blocks was also evaluated according to modified AWPA E11-99 standard test method of determining the leachability of wood preservatives. Leaching of CCA components from treated wood blocks with 1% EDTA solution for 14 days caused more copper leaching compared to leaching with deionized water. Leaching with 1% EDTA for 14 days removed 53% copper from the blocks whereas 14% copper was leached from the blocks with deionized water. The results suggest that EDTA extraction removes significant quantities of copper from CCA-treated wood. Thus, EDTA could be important in the remediation of wood waste treated with the newest formulations of organometalic copper compounds and other water-borne wood preservatives containing copper.     

Value addition of vegetable wastes by solid-state fermentation using Aspergillus niger for use in aquafeed industry

Vegetable waste typically has high moisture content and high levels of protein, vitamins and minerals. Its value as an agricultural feed can be enhanced through solid-state fermentation (SSF). Two experiments were conducted to evaluate the nutritional status of the products derived by SSF of a mixture of dried vegetable waste powder and oil cake mixture (soybean flour, wheat flour, groundnut oil cake and sesame oil cake at 4:3:2:1 ratio) using fungi Aspergillus niger S₁4, a mangrove isolate, and A. niger NCIM 616. Fermentation was carried out for 9 days at 35% moisture level and neutral pH. Significant (p < 0.05) increase in crude protein and amino acids were obtained in both the trials. The crude fat and crude fibre content showed significant reduction at the end of fermentation. Nitrogen free extract (NFE) showed a gradual decrease during the fermentation process. The results of the study suggest that the fermented product obtained on days 6 and 9 in case of A. niger S₁4 and A. niger NCIM 616 respectively contained the highest levels of crude protein.     

Fate and behavior of metal(loid) contaminants in an organic matter-rich shooting range soil: Implications for remediation

This study investigates the fate and behavior of lead (Pb), copper (Cu), antimony (Sb), and arsenic (As) in a shooting range soil. The soil samples were collected from the surface (0–15 cm) and the subsurface (15–40 cm and 40–55 cm) of a grassy and wood chip covered impact area behind a firing position. Optical microscopy images indicate significant amounts of corroded bullet fragments and organic wood chips in the surface soil. Analysis by X-ray powder diffraction (XRPD) and scanning electron microscopy electron dispersive X-ray spectroscopy (SEM-EDS) showed that metallic Pb was transformed into lead oxides (litharge PbO and massicot PbO) and lead carbonates (hydrocerussite Pb₃(CO₃)₂(OH)₂, cerussite PbCO₃, and plumbonacrite Pb₅(CO₃)₃O(OH)₂). Rietveld quantification indicated the surface soil contained 14.1% metallic Pb, 17.9% hydrocerussite, 5.2% plumbonacrite, 5.9% litharge, and 3.9% massicot on a dry weight basis, or a total of 39.7% Pb, far in excess of lead concentrations typically found in US shooting range soils. Metallic Cu (bullet jacket material) appeared stable as no secondary minerals were detected in the surface soil. As and Sb concentrations were on the order of 1,057 mg/kg and 845 mg/kg respectively. The elevated soil pH coupled with high organic carbon content is thought to have caused downward migration of metals, especially for Pb, since 4,153 mg Pb/kg was observed at a depth of 55 cm. More than 60% of Pb was concentrated in the coarse soil (> 0.425 mm) fraction, suggesting soil clean-up possible by physical soil washing may be viable. The concentrations of Pb, As, and Sb in the toxicity characteristic leaching procedure (TCLP) extracts were 8,869 mg/L, 6.72 mg/L, and 6.42 mg/L respectively, were above the USEPA non-hazardous regulatory limit (As and Pb) of 5 mg/L. The elevated Sb and As concentrations draw concern because there is historically limited information concerning these metals at firing ranges and several values exceeded local soil cleanup criteria. As the high Pb concentrations appeared to be linked to the presence of organic-rich berm cover materials, the use of wood chips as berm cover to prevent soil erosion requires reconsideration as a shooting range management practice.     

Heavy metals in source-separated compost and digestates

The production of compost and digestate from source-separated organic residues is well established in Europe. However, these products may be a source of pollutants when applied to soils. In order to assess this issue, composts, solid and liquid digestates from Switzerland were analyzed for heavy metals (Cd, Co, Cr, Cu, Ni, Pb and Zn) addressing factors which may influence the concentration levels: the treatment process, the composition, origin, particle size and impurity content of input materials, the season of input materials collection or the degree of organic matter degradation.Composts (n = 81) showed mean contents being at 60% or less of the legal threshold values. Solid digestates (n = 20) had 20–50% lower values for Cd, Co, Pb and Zn but similar values for Cr, Cu and Ni. Liquid digestates (n = 5) exhibited mean concentrations which were approximately twice the values measured in compost for most elements. Statistical analyses did not reveal clear relationships between influencing factors and heavy metal contents. This suggests that the contamination was rather driven by factors not addressed in the present study.According to mass balance calculations related to Switzerland, the annual loads to agricultural soils resulting from the application of compost and digestates ranged between 2% (Cd) and 22% (Pb) of total heavy metal loads. At regional scale, composts and digestates are therefore minor sources of pollution compared to manure (Co, Cu, Ni, Zn), mineral fertilizer (Cd, Cr) and aerial deposition (Pb). However, for individual fields, fertilization with compost or digestates results in higher heavy metal loads than application of equivalent nutrient inputs through manure or mineral fertilizer.     

Leaching of heavy metals from chromated copper arsenate (CCA) treated wood after disposal

Wood treated by preservatives is commonly found in solid waste. Among the different types of preserved wood, chromated copper arsenate (CCA) treated wood recently has received much attention due to the scale of usage and its significant role in soil and water contamination. As the ash of CCA treated wood would be hazardous if the wood were to be incinerated, this is not a good alternative, and the best available disposal method is thus landfilling in the US, Canada and Australia. Leaching of the metals from preserved wood that is disposed in unlined landfills for construction debris pollutes the soil and water environments. Several factors affecting leaching of the metals from wood, including pH of the leachant, temperature, the duration of leaching and the type of leachant, were investigated. These factors affect each of the metals, chromium, copper and arsenic, differently. A comparison of these effects on each metal was performed. The results of the experiments showed that the pH of the leachants has a significant effect on the leaching process, and sulfuric acid (pH 3) is the most effective leachant compared to nitric and acetic acid (pH 3-4-5). The amounts of leached chromium, copper and arsenic by sulfuric acid (pH 3) during 15 days were, respectively, 0.2, 0.14 and 0.15 mg more than leachates by nitric acid (pH 5) on the basis of 1g of wood (initial contents of 1.03 mg, 0.42 g and 0.8 mg per g of wood). Most of the leaching occurs in the first 5 days, and the rate of leaching decreases significantly after 5 days. Increasing temperature increases the amount of leached metals, and arsenic is the least resistant metal to the leaching when the temperature increases. Increasing the temperature from 15 degrees C to 35 degrees C during 15 days increases the amount of leached chromium, copper and arsenic by acetic acid at pH 5 by about 0.1, 0.4 and 1.2mg per g of wood, respectively.     

Recovery of metals from waste printed circuit boards by supercritical water pre-treatment combined with acid leaching process

Waste printed circuit boards (PCBs) contain a large number of metals such as Cu, Sn, Pb, Cd, Cr, Zn, and Mn. In this work, an efficient and environmentally friendly process for metals recovery from waste PCBs by supercritical water (SCW) pre-treatment combined with acid leaching was developed. In the proposed process, waste PCBs were pre-treated by SCW, then the separated solid phase product with concentrated metals was subjected to an acid leaching process for metals recovery. The effect of SCW pre-treatment on the recovery of different metals from waste PCBs was investigated. Two methods of SCW pre-treatment were studied: supercritical water oxidation (SCWO) and supercritical water depolymerization (SCWD). Experimental results indicated that SCWO and SCWD pre-treatment had significant effect on the recovery of different metals. SCWO pre-treatment was highly efficient for enhancing the recovery of Cu and Pb, and the recovery efficiency increased significantly with increasing pre-treatment temperature. The recovery efficiency of Cu and Pb for SCWO pre-treatment at 420 °C was 99.8% and 80%, respectively, whereas most of the Sn and Cr were immobilized in the residue. The recovery of all studied metals was enhanced by SCWD pre-treatment and increased along with pre-treatment temperature. Up to 90% of Sn, Zn, Cr, Cd, and Mn could be recovered for SCWD pre-treatment at 440 °C.     

Rapid-extraction oxidation process to recover and reuse copper chromium and arsenic from industrial wood preservative sludge

Chromated copper arsenate (CCA) wood preservative can form insoluble sludges when the hexavalent chromium component is reduced by wood extractives, wood particles and preservative additives in the solution. This sludge accumulates in treating solution work tanks, sumps and in-line filters and must be disposed of as hazardous wastes by waste disposal companies at high costs. A number of commercial sludges were investigated and found to contain 18-94% copper, chromium and arsenic as oxides combined with sand, oil, wood particles, additives and wood extractives. We have developed a multi-stage recycling process whereby approximately 97% of the CCA components are recovered from the sludge. It involves extraction with sodium hypochlorite to remove and oxidize chromium (more than 90%) and extract most of the arsenic (approx. 80%) followed by extraction of the copper and remaining arsenic and chromium with phosphoric acid. The phosphoric acid extract contains some trivalent chromium, which is subsequently oxidized by sodium hypochlorite. The combined oxidized extract containing CrVI, CuII and AsV was compatible with CCA treating solutions and could be re-used commercially for treating wood without having a significant effect on the preservative fixation rate or the leach resistance of the treated wood. A cost analysis showed that the economic savings from recovery of CCA chemicals and reduced landfill costs exceeded the variable costs for materials and energy for the process by as much as Can $966 per tonne of sludge if sodium sulfite can be acquired in bulk quantities for the process.     

Removal of mixed contaminants by Fe0-based biobarrier in flow-through columns using recycled waste materials

The present study investigated the reactivity and ability of permeable reactive barriers [zero-valent iron (ZVI)-barrier plus biobarrier) to remove various contaminants (Cd, As, Zn, Cu, Mn, Cr, NO₃ ⁻, NH₄ ⁺, and COD_cr) from synthetic leachate. Two different reactive materials were used in this study, namely ZVI and autoclaved lightweight concrete (ALC). After 90 days of column operation, the contaminant profiles were determined along the length of the columns. The heavy metals were extensively removed in the bio-ALC and sequential barriers (ZVI plus bio-ALC), however the removal efficiencies for the heavy metals Zn and Cr in the ALC and bio-ALC barriers were comparatively low. Nitrate was completely removed (>99.9%) in the ALC, bio-ALC, and sequential barriers. More than 50% of the produced ammonium and organic materials were removed in the biologically reactive zone of the sequential barriers. The results of the present study suggest that sequential barriers are one of the best solutions for in situ remediation and that they can be applied to clean up the leachate released from landfills.     

Use Of Peat Extract In The Ensiling Of Fisheries Wastes

Fish processing wastes, namely minced cod (Gadus morhua) offal and minced male capelin (Mallotus villosus), were used in two kinds of ensiling (silage making) processes. In one process they were ensiled by the direct addition of acids, and in the other they were ensiled using various carbohydrate sources and bacterial cultures to produce organic acids in situ. Ensiled material was analysed for various components at times throughout its storage period, and monitored for onset of spoilage. It was found that neither prior freezing nor initial heat treatment of capelin had an effect on the preservation effectiveness of the ensiling process. It was concluded that both the addition of formic acid to cod offal and the fermentation of lactic acid bacteria are effective methods of ensiling this material. Peat extracts with a relatively high carbohydrate content were found to be a satisfactory source of carbohydrates for the fermentation of lactic acid bacteria in cod offal silage. However, peat extracts with a relatively low pH were found to be unsatisfactory as a direct source of acid for ensiling.     

An advanced study on the hydrometallurgical processing of waste computer printed circuit boards to extract their valuable content of metals

This study refers to two chemical leaching systems for the base and precious metals extraction from waste printed circuit boards (WPCBs); sulfuric acid with hydrogen peroxide have been used for the first group of metals, meantime thiourea with the ferric ion in sulfuric acid medium were employed for the second one. The cementation process with zinc, copper and iron metal powders was attempted for solutions purification. The effects of hydrogen peroxide volume in rapport with sulfuric acid concentration and temperature were evaluated for oxidative leaching process. 2 M H₂SO₄ (98% w/v), 5% H₂O_2, 25 °C, 1/10 S/L ratio and 200 rpm were founded as optimal conditions for Cu extraction. Thiourea acid leaching process, performed on the solid filtrate obtained after three oxidative leaching steps, was carried out with 20 g/L of CS(NH₂)₂, 6 g/L of Fe³⁺, 0.5 M H₂SO₄, The cross-leaching method was applied by reusing of thiourea liquid suspension and immersing 5 g/L of this reagent for each other experiment material of leaching. This procedure has lead to the doubling and, respectively, tripling, of gold and silver concentrations into solution. These results reveal a very efficient, promising and environmental friendly method for WPCBs processing.     

Sources of heavy metal contamination in Swedish wood waste used for combustion

In this paper, wood waste (RWW) recovered for heat production in Sweden was studied. Previous research has concluded that RWW contains elevated amounts of heavy metals, causing environmental problems during waste management. This study extends previous work on RWW by analysing which pollution sources cause this contamination. Using existing data on the metal contents in various materials, and the amounts of these materials in RWW, the share of the elevated amounts of metals in RWW that these materials explain was quantified. Six different materials occurring in RWW were studied and the results show that they explain from 70% to 100% of the amounts of arsenic, chromium, lead, copper and zinc in RWW. The most important materials contributing to contamination of RWW are surface-treated wood, industrial preservative-treated wood, plastic and galvanised fastening systems. These findings enable the development and evaluation of strategies aiming to decrease pollution and resource loss from handling RWW. It is argued that source separation and measures taken further downstream from the generation site, such as treatment, need to be combined to substantially decrease the amount of heavy metals in RWW.