The wood preservative chromated copper arsenate is a substrate for trimethylarsine biosynthesis

The wood preservative chromated copper arsenate (CCA) is a very widely used product. As it contains both copper and arsenic, it is not dissimilar to the pigments Scheele's green and Schweinfurter's green which were found to be biologically convertible to the toxic Gosio gas (B. Gosio, Ber. 30:1024-1026, 1897) later identified by Challenger and co-workers as trimethylarsine (F. Challenger, Adv. Enzymol. 12:429-491, 1951). Thus, it was of interest to determine whether microbiological action on CCA and wood treated with CCA could result in the production of trimethylarsine. We report that the fungus Candida humicola will produce this arsine from dilute solutions of CCA and from wood soaked in CCA.     

Removal of CCA from treated wood by oxalic acid extraction, steam explosion, and bacterial fermentation

Most preservative-treated wood produced and consumed in the United States is treated with toxic inorganic compounds containing copper, chromium, and arsenic. Because chromated copper arsenate (CCA) is fixed to the wood, CCA-treated wood has not been considered toxic or hazardous and it is currently disposed of in approved landfills. Growing public concern about environmental contamination from treated wood combined with the removal of greater quantities of CCA-treated wood from service have presented a disposal challenge for this fiber source. In this study, CCA-treated wood was processed by acid extraction, steam explosion, and bacterial fermentation and evaluated for removal of copper, chromium, and arsenic. Copper was the easiest to remove by these treatments and chromium the most resistant to removal. Exposing CCA-treated wood to steady-state bacterial growth by continuous culture with Bacillus licheniformis CC01 did not enhance removal of CCA components compared to standard mixed culture when acid extraction preceded bacterial fermentation. Nor did steam explosion, alone or in conjunction with acid extraction and bacterial fermentation, enhance removal of CCA components; the chromium and arsenic components resisted removal. Grinding CCA-treated wood chips into 20-mesh sawdust provided greater access to and removal of CCA components by all processes. However, grinding the chips was unnecessary if they were treated with acid prior to bacterial fermentation. Extraction with oxalic acid as a precursor to bacterial fermentation with B. licheniformis CC01 removed 90% copper (CuO), 80% chromium (CrO₃), and 100% arsenic (As₂O₅) from treated chips. The combination of acid extraction and bacterial fermentation removed 80–100% of these metals from CCA-treated wood. Received 15 December 1997/ Accepted in revised form 08 March 1998     

Removal of copper, chromium, and arsenic from CCA-treated wood onto chitin and chitosan

Chitin and chitosan are naturally abundant biopolymers which are of interest to research concerning the sorption of metal ions since the amine and hydroxyl groups on their chemical structures act as chelation sites for metal ions. This study evaluates the removal of copper, chromium, and arsenic elements from chromated copper arsenate (CCA)-treated wood via biosorption by chitin and chitosan. Exposing CCA-treated sawdust to various amounts of chitin and chitosan for 1, 5, and 10 days enhanced removal of CCA components compared to remediation by deionized water only. Remediation with a solution containing 2.5 g chitin for 10 days removed 74% copper, 62% chromium, and 63% arsenic from treated sawdust. Remediation of treated sawdust samples using the same amount of chitosan as chitin resulted in 57% copper, 43% chromium, and 30% arsenic removal. The results suggest that chitin and chitosan have a potential to remove copper element from CCA-treated wood. Thus, these more abundant natural amino polysaccharides could be important in the remediation of waste wood treated with the newest formulations of organometallic copper compounds and other water-borne wood preservatives containing copper.     

Effects of CCA (copper-chrome-arsenic) preservative treatment of wood on the settlement and recruitment of barnacles and tube building polychaete worms

The effect of the anti-marine-borer treatment of wood using CCA (a pressure impregnated solution of copper, chromium and arsenic compounds) on non-target fouling animals was investigated. Panels treated to target retentions of 12, 24 and 48 kg CCA m(-3) of wood, together with untreated controls were exposed for 6, 12 and 18 months at coastal sites in Greece, Portugal, France and Sweden. General linear model (GLM) analysis revealed significant increases in numbers of certain fouling organisms (the serpulids Ficopomatus enig-maticus, Hydroides spp., Pomatoceros lamarkii and an unidentified species, three species of spirorbid, and the balanids Balanus perforatus and Elminius modestus) with increase in retention of CCA. The effect of CCA on the numbers of recruits may be due to effects on their settlement and survival, but may also be due to suppression of competitors. Significant differences in settlement density of barnacle spat occurred on newly exposed wood and on wood that had been exposed for 6 and 18 months. The relationships between settlement density and retention could be described by logarithmic curves of the form settlement density = a 1n(l + retention)+b. The effects of CCA on settlement are ascribed either to modification of wood surface chemistry leading to changes in surface charge, the availability of Cu, Cr or As at the wood surface, or to modifications to the microbial film. Barnacle settlement was between 6.5 and 14 times more intense on latewood than on earlywood, an effect that was evident in both untreated and preservative-treated wood.     

Leachability,metal corrosion,and termite resistance of wood treated with copper-based preservative

Health-awareness and concern for the environment have resulted in voluntary removal of chromated copper arsenate (CCA) from wood preservatives in residential applications worldwide. Copper-based preservatives have been formulated as replacements, but these may not provide a permanent solution to all of the related problems, including copper contamination of aquatic environments and corrosion of fasteners. In this study, the copper retention (before and after the leaching process) of five softwood specimens vacuum-treated with alkaline copper quaternary (ACQ) and copper azole (CA) at three target retention levels was investigated by X-ray fluorescence studies. The metal corrosion and termite (Coptotermes formosanus) resistance of treated specimens were studied under laboratory conditions. Except for treated Japanese larch wood, the copper retention levels of the other wood specimens were able to meet the target copper retention values (use classes 2–4) in Chinese National Standard 3000. The copper leaching rates were 6.92–19.54% for ACQ-treated wood and 9.38–22.46% for CA-treated wood. The metal corrosion rates of iron nails due to corrosion tests (CNS 6717) were influenced significantly by the 1.2% ACQ and 1.2% CA treatments; whereas the metal corrosion rates of zinc-galvanized steel nails were less than 2 and could meet the tested standard. Even though the ACQ and CA treatments caused higher copper leaching rates from the treated specimens, they also increased termite mortalities and reduced the mass loss significantly after termite-resistance tests (JIS K 1571).     

Experiments to determine the effect of certain wood preservatives on the growth and cropping of the cultivated mushroom (Psalliota campestris)

A small-scale laboratory method of determining the effect of wood preservatives on growth and cropping of the cultivated mushroom is outlined. Experiments with a number of well-known wood preservatives are described. According to these experiments wood treated with the following preservatives had no adverse effect on mycelial growth or on croppings: 5 % copper sulphate solution, green Cuprinol, 5 % Celcure solution, 2 % Triolith (Wolman salts) solution. On the other hand, wood treated with 2 % Chromel salt and coal-tar creosote reduced the vigour of growth of mushroom mycelium to a depth of 1/2 in. in compost that was in contact with it. Under these conditions, however, the mycelium was not killed nor was the cropping reduced even when the treated wood was only 1 1/2 in in. below the casing soil. As in all experiments the treated wood was covered with compost, the chance of vapours from the preservatives coming into contact with sporophores was very small, and the possibility of harmful effect in mushroom houses from such vapours should not be ignored.
The experiments indicate that full-scale trials in commercial mushroom houses could be undertaken with copper sulphate, green Cuprinol, Celcure and Triolith with negligible risk to the crop, but that it is advisable to carry out trials on a smaller scale with Chromel and coal-tar creosote of known composition to determine whether these preservatives have any adverse effect on cropping. Owing to the great range in composition shown by coal-tar creosote it is most important that the conclusions reached with the particular sample used in the above experiments should not be applied to creosotes in general.     

Studies on preservative tolerant Phialophora species

Phialophora species are shown to possess a variable capacity for growth on either copper, arsenic or copper-chrome-arsenic (CCA) supplemented laboratory media. The most copper tolerant species. Phialophora sp. A, P. malorum and P. mutabilis, were also the most arsenic resistant. Fine structural studies have shown intra- and to a lesser extent extracellular localization of copper which may provide a means of tolerating high external copper levels under culture conditions. Wood decay experiments have shown Phialophora spp. to have a good capacity to degrade K33 treated birch after 7·5 months but not pine, despite colonization. The most important wood degrading Phialophora were also the more copper/arsenic resistant species although non-tolerant species were also able to degrade treated birch. A comparison between the extreme copper levels tolerated by selected species with the amount of copper in treated wood may suggest that only sub-toxic levels may be obtained, levels which may not require special detoxification mechanisms for either colonization or decay in wood. In this respect, factors other than toxicity, particularly the nature of the substrate (e.g. lignin type and level) and reaction with CCA and ammoniacal-copper during treatment may be of greater significance.     

Enhanced extraction of heavy metals in the two-step process with the mixed culture of Lactobacillus bulgaricus and Streptococcus thermophilus

For biological extraction of heavy metals from chromated copper arsenate (CCA) treated wood, different bacteria were investigated. The extraction rates of heavy metals using Lactobacillusbulgaricus and Streptococcusthermophilus were highest. The chemical extraction rates were depended on the amounts of pyruvic acid and lactic acid. Especially, the extraction rates using mixed pyruvic acid and lactic acid were increased compared to those of sole one. They were also enhanced in the mixed culture of L. bulgaricus and S. thermophilus. To improve the extraction of CCA, a two-step processing procedure with the mixed culture of L. bulgaricus and S. thermophilus was conducted. A maximum of 93% of copper, 86.5% of chromium, and 97.8% of arsenic were extracted after 4 days. These results suggest that a two-step process with the mixed culture of L. bulgaricus and S. thermophilus is most effective to extract heavy metals from CCA treated wood.     

Chromium,Copper, and Arsenic Concentrations in Soil Underneath CCA-Treated Wood Structures

Soils below nine structures (decks and foot bridges) in Florida were examined to evaluate potential impacts from chromated copper arsenate (CCA), a common wood preservative. Eight of the nine structures were confirmed to have been treated with CCA. Soils collected were evaluated for arsenic, chromium, and copper concentrations as well as pH, volatile solids content and particle size distribution. Two types of soil samples were collected: a soil core and surface soil samples (upper 2.5 cm). One soil core was collected from below each deck and one control core was collected from an area removed from one of the structures. Eight or nine surface soil samples were collected in a grid-like fashion from beneath each structure. Equal numbers of surface control samples were collected from areas away from the structures. Metal concentrations were elevated in both the soil cores and surface samples collected from below the CCA-treated structures. Core samples showed elevated concentrations of metals at depths up to 20 cm. The arithmetic mean concentrations of arsenic, chromium, and copper in the 65 surface soil samples collected from below CCA-treated structures were 28.5 mg/kg, 31.1 mg/kg, and 37.2 mg/kg, respectively, whereas the mean concentrations of arsenic, chromium, and copper in the control samples were 1.34 mg/kg, 8.62 mg/kg, and 6.05 mg/kg, respectively. Arsenic concentrations exceeded Florida's risk-based soil cleanup target level (SCTL) for residential settings in all 65 surface soil samples. The industrial setting SCTL was exceeded in 62 of the 65 samples.     

Characterization of a strong CCA-treated wood degrader,unknown <Emphasis Type="Italic">Crustoderma</Emphasis> species

In this study, basidiomycete isolates that possessed a strong ability to degrade chromated copper arsenate (CCA)-treated wood were characterized. These fungal isolates, which were collected from CCA-treated pine log wastes, showed no recognizable morphological properties on culture media. Nucleotide sequence analysis of the large subunit rDNA of the isolates revealed that they were one species. Based on the high sequence similarity (>95%) and close phylogenetic relationship with several known species of Crustoderma, the fungal isolates characterized in this study were classified as a Crustoderma sp. In a wood degradation test, Crustoderma isolate KUC8611 produced a remarkably higher weight loss in CCA-treated Pinus radiata (68.7%), Pseudotsuga menziesii (39.7%), and Tsuga heterophylla (38.5%) wood than other evaluated basidiomycete species, including Crustoderma flavescens and Crustoderma corneum. In addition, extracellular enzymes for cellulose and protein degradation were detected when the isolates were cultured in chromogenic media, which supports the finding that isolate KUC8611 is a wood degrader. Furthermore, an in vitro test for metal tolerance revealed that isolate KUC8611 showed strong arsenic tolerance, but that it could not tolerate copper. Finally, isolate KUC8611 produced lower amounts of oxalic acid than copper-tolerant fungi such as Fomitopsis palustris and Antrodia vaillantii. To the best of our knowledge, this is the first study to report the degradation of CCA-treated wood by a Crustoderma species.     

Assessment of Potential Human Health Risks from Arsenic in CCA-Treated Wood

Chromated copper arsenate (CCA) is a chemical preservative used to treat wood for a variety of outdoor uses, including decks, fencing, and play structures. This article describes a methodology to quantify exposures to arsenic from CCA-treated wood. Exposure was evaluated for ingestion and dermal contact with arsenic-containing residue on treated wood surfaces (dislodgeable arsenic), and ingestion, dermal contact, and inhalation of soil containing arsenic originating from treated wood structures. Standard approaches were used to quantify exposures to arsenic in soil. In the absence of standard approaches for exposures to dislodgeable residue, an empirical approach was developed, extrapolating from studies of soil loadings on hands and soil ingestion rates to estimate the amount of dislodgeable residue on hands that is subsequently ingested. Results from animal studies were used to develop relative bioavailability estimates for dislodgeable and soil arsenic. A focused sensitivity analysis demonstrated that the assumptions used regarding hand loading and subsequent incidental ingestion of dislodgeable arsenic had the most significant impact on the results. This assessment indicates low uptake of arsenic into the body, resulting in incremental lifetime cancer risks within USEPA's target risk levels. We compare this approach to other methodologies used to assess exposures to treated wood.     

Degradation of arsenobetaine by microorganisms associated with marine macro algae,Monostroma nitidium and Hizikia fusiforme

• 1.1. Arsenobetaine-containing growth media (ZoBell 2216E; solution of inorganic salts) were mixed with each of two marine macro algae, a green alga Monostroma nitidum and a brown alga Hizikia fusiforme, as a source of microorganisms.
• 2.2. The conversion of arsenobetaine to trimethylarsine oxide and/or dimethylarsinic acid by the microorganisms associated with the marine macro algae was confirmed in both the media.
• 3.3. A striking contrast, however, in the conversion pattern was observed between the two algae: arsenobetaine was converted to trimethylarsine oxide and trimethylarsine oxide to dimethylarsine acid successively with M. nitidum, while the reverse was observed with H. fusiforme.

     

Phytoremediation of an arsenic-contaminated site using Pteris vittata L.: a two-year study

A field study was conducted to determine the efficiency of Chinese brake fern (Pteris vittata L.), an arsenic hyperaccumulator, on removal of arsenic from soil at an arsenic-contaminated site. Chinese brake ferns were planted on a site previously used to treat wood with chromated copper arsenate (CCA). Arsenic concentrations in surface and profile soil samples were determined for 2000, 2001, and 2002. In both 2001 and 2002, senesced and senescing fronds only, as well as all fronds, were harvested. Frond arsenic concentrations were not significantly different between the three harvests. Compared to senesced fronds, live fronds resulted in the greatest amount of arsenic removal. There were no significant differences in soil arsenic concentrations between 2000, 2001, and 2002, primarily due to the extreme variability in soil arsenic concentrations. However, the mean surface soil arsenic was reduced from 190 to 140 mg kg(-1). Approximately 19.3 g of arsenic were removed from the soil by Chinese brake fern. Therefore, this fern is capable of accumulating arsenic from the CCA -contaminated site and may be competitive, in terms of cost, to conventional remediation systems. However, better agronomic practices are needed to enhance plant growth and arsenic uptake to obtain maximum soil arsenic removal and to minimize remediation time.     

Nephrotoxicity effects of the wood preservative chromium copper arsenate on mice: Histopathological and quantitative approaches

Chromium copper arsenate (CCA) was used for the protection of wood building materials until the restriction by EPA in 2002.During a short period of time 14–24 h, a comparative nephrotoxicity study was performed regarding the effects of CCA and its compounds per se. Histopathological and histochemical features were correlated with the concentration of the total arsenic and chromium in mice kidney.Animals were subcutaneously injected with CCA (7.2 mg/kg arsenic and 10.2 mg/kg chromium per body weight), CrO₃ (10.2 mg/kg), As₂O₅ (7.2 mg/kg) and NaCl (0.9%) per se.The histopathological examination of the renal sections evidenced acute tubular necrosis in the groups of animals exposed to CCA (in both periods of time).Although the same contents of pentavalent arsenic and hexavalent chromium were injected in treated animals with CCA and with the prepared solutions of As₂O₅ and CrO₃, the arsenic concentration on kidneys of CCA-exposed animals was much higher than those in animals exposed to As₂O₅ (32- and 28-fold higher at 14 and 24 h, respectively). However, the elimination of chromium seems to occur similarly in the kidneys of animals treated with CCA and CrO₃ per se. Interactions among the components of CCA result in a marked decrease of the ability of kidney to eliminate simultaneously both analytes. The nephrotoxicity of CCA was higher than its components per se, evidencing a possible synergetic effect.     

Worldwide correlations of mechanical properties and green wood density

? Premise of the study: The density of wood is highly correlated with the ability of stems and roots to resist bending or twisting, which is important for evaluating the mechanical behavior of trees. It also provides a measure of carbon storage, which is an important variable in modeling ecosystem processes and tree construction costs. However, most measurements of the density and mechanical properties of wood have little direct bearing on understanding the biomechanics of living plants because they are based on kiln- or air-dried samples. ? Methods: Here, we present and analyze the relationships between four important mechanical properties (Young's modulus, the modulus of rupture, and the maximum strength in shearing and in compression) and the density of green wood (i.e., wood at 50% moisture content) from a worldwide, taxonomically broad spectrum of 161 species. ? Key results: These data indicate that each of the mechanical properties disproportionately increases across species with increasing green wood density, i.e., stems composed of denser green wood are disproportionately stiffer and stronger than stems with equivalent cross-sections composed of less dense green wood. ? Conclusions: Although denser wood may have a higher carbon construction cost, the mechanical benefits of denser woods likely outweigh the extra cost.     

Shear stress depends on vascular territory: comparison between common carotid and brachial artery.

Shear stress (SS) is thought to be constant throughout the vascular system. Evidence for this supposition is scarce, however. To verify this hypothesis in vivo, we assessed common carotid (CCA) and brachial artery (BA) peak and mean wall shear rate (SR) noninvasively in 10 healthy volunteers (23.7 +/- 3.4 yr) with an ultrasound SR estimation system. SS was estimated from SR and calculated whole blood viscosity. SR was higher (P < 0.05) in the CCA (mean: 359 +/- 111 s(-1); peak: 1,047 +/- 345 s(-1)) than in the BA (mean: 95 +/- 24 s(-1); peak: 770 +/- 170 s(-1)). Whole blood viscosity was higher in the BA than in the CCA (5.1 +/- 0.7 vs. 3.3 +/- 0.6 mPa. s; P < 0.001). Peak SS did not differ between the CCA and the BA, whereas mean SS was significantly higher in the CCA (1.15 +/- 0.21 Pa) than in the BA (0.48 +/- 0.15 Pa; P < 0.001). These results demonstrate that BA SS strongly deviates from CCA SS in vivo.     

The Hadal Amphipod Hirondellea gigas Possessing a Unique Cellulase for Digesting Wooden Debris Buried in the Deepest Seafloor

The Challenger Deep in the Mariana Trench is the deepest point in the ocean (10,994 m). Certain deep-sea animals can withstand the extreme pressure at this great depth. The amphipod Hirondellea gigas is a resident of the Challenger Deep. Amphipods are common inhabitants at great depths and serve as scavengers. However, there is relatively little information available regarding the physiology of H. gigas or this organism's ecological interactions in the hadopelagic zone. To understand the feeding behavior of this scavenger in the deepest oligotrophic hadal zone, we analyzed the digestive enzymes in whole-body extracts. We describe the detection of amylase, cellulase, mannanase, xylanase, and α-glycosidase activities that are capable of digesting plant-derived polysaccharides. Our identification of glucose, maltose, and cellobiose in the H. gigas extracts indicated that these enzymes function under great pressure in situ. In fact, the glucose content of H. gigas averaged 0.4% (w/dry-w). The purified H. gigas cellulase (HGcel) converted cellulose to glucose and cellobiose at an exceptional molar ratio of 2∶1 and efficiently produced glucose from dried wood, a natural cellulosic biomass, at 35°C. The enzyme activity increased under a high hydrostatic pressure of 100 MPa at 2°C, conditions equivalent to those found in the Challenger Deep. An analysis of the amino acid sequence of HGcel supported its classification as a family 31 glycosyl hydrolase. However, none of the enzymes of this family had previously been shown to possess cellulase activity. These results strongly suggested that H. gigas adapted to its extreme oligotrophic hadal oceanic environment by evolving digestive enzymes capable of digesting sunken wooden debris.     

福建龙岩城区园林树木木材密度和生材含水率研究

对福建龙岩城区栽植的30种园林树木测定木材基本密度、生材密度和生材含水率。结果表明,针叶树木材基本密度以柏木Cupressus funebris最高(0.636 g·cm-3),南洋杉Araucaria cunninghamii最低(0.462 g·cm-3);阔叶树以相思树Acacia confusa最高(0.757 g·cm-3),美丽异木棉Ceiba speciosa最低(0.228 g·cm-3)。生材密度针叶树竹柏Podocarpus nagi最高(0.975 g·cm-3),南洋杉最低(0.838 g·cm-3);阔叶树相思树最高(1.204 g·cm-3),石栗Aleurites moluccana最低(0.799 g·cm-3)。生材含水率针叶树竹柏最高(105%),柏木最低(30%);阔叶树以美丽异木棉最高(319%),光皮梾木Swida wilsoniana和木麻黄Casuarina equisetifolia最低,均为56%。南北两向的基本密度、生材密度和生材含水率差异不大。在距树皮8 cm范围内,基本密度和生材密度的径向变化模式可归纳为五种类型：(1)密度从髓心向树皮方向递增;(2)密度从髓心向树皮方向递减;(3)距树皮8 cm范围内密度变化不明显;(4)距树皮3～5 cm范围内密度较低;(5)距树皮3～5 cm范围内密度较高。生材含水率径向变化趋势仅限于上述前四种类型。     

Boron impregnation treatment of Eucalyptus grandis wood

Eucalyptus grandis is suitable for small timber purposes, but its wood is reported to be non-durable and difficult to treat. Boron compounds being diffusible, and the vacuum-pressure impregnation (VPI) method being more suitable for industrial-scale treatment, the possibility of boron impregnation of partially dry to green timber was investigated using a 6% boric acid equivalent (BAE) solution of boric acid and borax in the ratio 1:1.5 under different treatment schedules. It was found that E. grandis wood, even in green condition, could be pressure treated to desired chemical dry salt retention (DSR) and penetration levels using 6% BAE solution. Up to a thickness of 50mm, in order to achieve a DSR of 5 kg/m(3) boron compounds, the desired DSR level as per the Indian Standard for perishable timbers for indoor use, it was found that neither the moisture content of wood nor the treatment schedule posed any problem as far as the treatability of E. grandis wood was concerned.