Monitoring losses of copper based wood preservatives in the Thames estuary

Field trials were conducted at two sites in the Thames estuary to monitor losses of copper, chromium and arsenic from wood preservative treated timbers of varying sizes and treatment regimes. Results indicated that leaching tests conducted under standard laboratory conditions might overestimate losses compared to losses resulting from real environmental exposures. Amine copper treated wood was noted to leach higher levels of copper compared to chromated copper arsenate treated wood, and was therefore considered an inappropriate replacement biocide for fresh and marine construction purposes on this basis. Increases in copper concentrations in the outer sections of amine copper treated posts may have represented re-distribution of this component in this timber. No accumulation of metals was found in sediments surrounding field trial posts.     

Evaluation of the critical factors controlling stability of chromium, copper, arsenic and zinc in iron-treated soil

Various environmental factors are expected to affect the mobility of elements in chemically stabilized soils. The aim of this study was to evaluate the effects of pH, oxidizing-reducing potential (Eh), liquid-to-solid ratio (L/S), presence of organic matter (OM) and microbial activity (MA) on the mobility of chromium, copper, arsenic and zinc in zerovalent iron (Fe(0))-stabilized soil. A 2(5) full factorial design was applied to assess the leaching of the elements from the treated soil. The factor having the most impact on the mobility of Cr, Cu and Zn was pH; low pH (3) led to the release of these elements. Arsenic remobilization was controlled by L/S and MA, whilst Eh, though also significant, had less influence. In the identified worst-case scenarios, more than half of the total Zn and Cu and 14% of As can be expected to remobilize from the treated soil. The leaching procedure concerning sample agitation and type of filtration showed to substantially affect the results of As leaching, especially in OM rich soil.     

Cu,Cr and As distribution in soils adjacent to pressure-treated decks,fences and poles

Chromated copper arsenate (CCA)-treated wood has been widely used in the Southeastern United States to protect wood products from microbial and fungal decay. The aims of this study were to (1). determine the distribution of arsenic (As), chromium (Cr), and copper (Cu), in soils surrounding CCA-treated wood structures such as decks, fences and poles; and (2). evaluate the impacts of these structures on As, Cr and Cu loading of the soils. Profile and lateral soil samples were collected under CCA-treated decks and adjacent to poles and fences. The results showed elevation of As, Cr and Cu concentrations close to and under the structures, with mean As concentrations as high as 23 mg x kg(-1) close to utility poles compared with less than 3 mg x kg (-1) at distances of about 1.5 m away. Concentrations of As, Cr, and Cu decreased with depth in areas close to CCA-treated poles. However, these results were only apparent in relatively new structures. A combination of weathering and leaching with time may have reduced the impact in older poles. Increased concentrations of As, Cu and Cr were also observed close to CCA-treated decks and fences, with age showing a similar impact. These results are helpful for CCA-treated wood product users to determine the safe use of these structures.     

Leaching of chromated copper arsenate wood preservatives: a review

Recent studies have generated conflicting data regarding the bioaccumulation and toxicity of leachates from preservative-treated wood. Due to the scale of the wood preserving industry, timber treated with the most common preservative, chromated copper arsenate (CCA), may form a significant source of metals in the aquatic environment. The existing literature on leaching of CCA is reviewed, and the numerous factors affecting leaching rates, including pH, salinity, treatment and leaching test protocols are discussed. It is concluded from the literature that insufficient data exists regarding these effects to allow accurate quantification of leaching rates, and also highlights the need for standardised leaching protocols.     

Modeling batch leaching behavior of arsenic and selenium from bituminous coal fly ashes

Correctly predicting the leaching potential of arsenic (As) and selenium (Se) is critical for assessing the environmental impact of coal fly ash. This study investigated the impacts of several key environmental factors, including pH, leaching time, and ash washing on the batch leaching behavior of As and Se from bituminous coal fly ashes. The experimental results demonstrated that As and Se leaching from fly ash increased beyond the minimal leaching pH ranges. Increasing leaching time increased As leaching but decreased Se leaching in the alkaline pH condition. A speciation-based adsorption model was used to quantify the batch leaching data, and determine the intrinsic leaching parameters including the total batch leachable mass and the adsorption constant of As or Se. The modeling approach was validated by correctly predicting the independent batch leaching data in a broad pH range and a different L/S condition. Experimental and modeling results also demonstrated that ash washing and ash aging (longer leaching time) did not change the adsorption constants of As and Se on the ash surface. However, ash washing could increase the availability of As and Se for leaching.     

Elemental analysis of ash residue from combustion of CCA treated wood waste before and after electrodialytic extraction

Element distribution in a combined fly ash and bottom ash from combustion of copper chromate arsenate (CCA) treated wood waste was investigated by scanning electron microscopy (SEM/EDX) before and after electrodialytic extraction. The untreated ash contained various particles, including pieces of incompletely combusted wood rich in Cr and Ca, and irregular particles rich in Si, Al and K. Cr was also found incorporated in silica-based matrix particles. As was associated with Ca in porous (char) particles, indicating that Ca-arsenates had been formed during combustion. Cu was associated with Cr in the incompletely combusted wood pieces and was also found in almost pure form in a surface layer of some matrix particles - indicating surface condensation of volatile Cu species. In treated ash, Ca and As were no longer found together, indicating that Ca-arsenates had been dissolved due to the electrodialytic treatment. Instead particles rich in Ca and S were now found, indicating precipitation of Ca-sulphates due to addition of sulphuric acid in connection with the electrodialytic treatment. Cu and Cr were still found associated with incompletely combusted wood particles and incorporated in matrix particles. Chemical analyses of untreated and treated ash confirmed that most As, but only smaller amounts of Cu and Cr was removed due to the electrodialytic extraction. Overall metal contents in the original ash residue were: 1.4 g As, 2.76 g Cu and 2.48 g Cr, after electrodialytic extraction these amounts were reduced by 86% for As, 15% for Cu and 33% for Cr.     

Leaching behavior of Cr(III) in stabilized/solidified soil

The leaching behavior of chromium was studied using batch leaching tests, surface complexation modeling and X-ray absorption near edge structure (XANES) spectroscopy. A contaminated soil sample containing 1330 mg-Cr kg(-1) and 25600 mg-Fe kg(-1) of dry soil was stabilized/solidified (S/S) with 10% cement, 25% cement, 10% lime and a mixture of 20% flyash and 5% lime. The XANES analysis showed that Cr(III) was the only Cr species in untreated soil and S/S-treated samples. The leachate Cr concentration determined using the toxicity characteristic leaching procedure (TCLP) was reduced from 5.18 mg l(-1) for untreated soil to 0.84 mg l(-1) for the sample treated with 25% cement. The Cr leachability in untreated and treated soil samples decreased dramatically as the pH increased from 3 to 5, remained at similar levels in the pH range between 5 and 10.5, and further decreased at pH>10.5. Modeling results indicated that the release of Cr(III) was controlled by adsorption on iron oxides at pH<10.5, and by precipitation of Ca(2)Cr(2)O(5).6H(2)O at pH>10.5.     

Supercritical water oxidation of tannery sludge: Stabilization of chromium and destruction of organics

The supercritical water oxidation (SCWO) of industrial tannery sludge was investigated to understand the simultaneous destruction of organic pollutants and recovery of high content chromium. Experiments were performed in a batch reactor at temperatures of 350–500 °C, reaction time of 150–300 s and different oxygen ratios, to exhibit the effect of operation conditions. Results showed that removal efficiency of chemical oxygen demand (COD) increased with higher temperature, larger oxidant amount and reaction time; a maximum value of 96% was obtained. Meanwhile, destruction yield was much higher under supercritical conditions than that in subcritical water. In addition, removal efficiency of Cr from sludge reached more than 98% under all conditions; higher temperature played a positive role. Further, leaching toxicity tests of heavy metals in solid products were conducted based on toxicity characteristic leaching procedure. All heavy metals except nickel showed a greatly reduced leaching toxicity through their stabilization. The chromium oxide recovered in ash was amorphous below 550 °C, so that the structure of Cr could not be identified by X-ray diffraction pattern. Special attention should be paid on nickel as its leaching toxicity increased due to the corrosion of reactor surface under severe reaction conditions.     

Amendment of arsenic and chromium polluted soil from wood preservation by iron residues from water treatment

An iron-rich water treatment residue (WTR) consisting mainly of ferrihydrite was used for immobilization of arsenic and chromium in a soil contaminated by wood preservatives. A leaching batch experiment was conducted using two soils, a highly contaminated soil (1033 mg kg⁻¹ As and 371 mg kg⁻¹ Cr) and slightly contaminated soil (225 mg kg⁻¹ As and 27 mg kg⁻¹ Cr). Compared to an untreated reference soil, amendment with 5% WTR reduced leaching in the highly contaminated soil by 91% for Cr and 98% for As. No aging effect was observed after 103 d. In a small field experiment, soil was mixed with 2.5% WTR in situ. Pore water was extracted during 3 years from the amended soil and a control site. Pore water arsenic concentrations in the amended soil were more than two orders of magnitude lower than in the control for the upper samplers. An increased release of arsenic was observed during winter in both fields, mostly in the deepest samplers. This is likely due to the formation of a pseudo-gley because of precipitation surplus. Stabilization of arsenic and chromium contaminated soil using WTR is a promising method but the transformation of ferrihydrite in soil proves a concern in case of waterlogged soils. Still the amendment minimized the leaching of arsenic, even in cases of seasonal releases.     

Impact of water saturation level on arsenic and metal mobility in the Fe-amended soil

The impact of water saturation level (oxidizing-reducing environment) on As and metal solubility in chromium, copper, arsenic (CCA)-contaminated soil amended with Fe-containing materials was studied. The soil was mixed with 0.1 and 1 wt% of iron grit (Fe(0)) and 1, 7 and 15 wt% of oxygen scarfing granulate (OSG, a by-product of steel processing). Solubility of As and metals was evaluated by a batch leaching test and analysis of soil pore water. Soil saturation with water greatly increased As solubility in the untreated as well as in the Fe-amended soil. This was related to the reductive dissolution of Fe oxides and increased concentration of As(III) species. Fe amendments showed As reducing capacity under both oxic and anoxic conditions. The cytotoxicity of the soil pore water correlated with the concentration of As(III). The Fe-treatments as well as water saturation of soil were less significant for the solubility of Cu, Cr and Zn than for As. The batch leaching test used for waste characterization substantially underestimated As solubility that could occur under water-saturated (anaerobic) conditions. In the case of soil landfilling, other techniques than Fe-stabilization of As containing soil should be considered.     

污水污泥中重金属污染物的溶出过程研究

污水污泥中污染物尤其是重金属的水体浸出作为重要的二次污染途径备受关注。为了探讨污水污泥中重金属的溶出规律,对上海7个污水处理厂的污水污泥进行了重金属总量分析,并采用水平振荡法对上述污水污泥中重金属进行了溶出动力学研究。结果表明,污水污泥中Cu、Cr和Zn的含量均较高,之后依次是Pb、As、Cd和Hg;污水污泥中重金属溶出动力学过程分为快速反应和慢速反应两个过程,可以用Elovich方程进行模拟;污水污泥中各重金属的溶出负荷差异较大,Cu、Cr和Zn的溶出负荷较大,其他较小,但各重金属相对于污水污泥中重金属总量的溶出百分比差异不大,基本处于10%以下。     

Assessment of zerovalent iron for stabilization of chromium, copper, and arsenic in soil

Stabilization of soil contaminated with trace elements is a remediation practice that does not reduce the total content of contaminants, but lowers the amounts of mobile and bioavailable fractions. This study evaluated the efficiency of Fe(0) to reduce the mobility and bioavailability of Cr, Cu, As and Zn in a chromated copper arsenate (CCA)-contaminated soil using chemical, biochemical and biotoxicity tests. Contaminated soil was stabilized with 1% iron grit. This treatment decreased As and Cr concentrations in leachates (by 98% and 45%, respectively), in soil pore water (by 99% and 94%, respectively) and in plant shoots (by 84% and 95%, respectively). The stabilization technique also restored most of analyzed soil enzyme activities and reduced microbial toxicity, as evaluated by the BioTox test. After stabilization, exchangeable and bioaccessible fractions of Cu remained high, causing some residual toxicity in the treated soil.     

镍渣的重金属浸出特性

在分析镍渣的矿物相组成和重金属元素含量的基础上,鉴定了镍渣样品的浸出毒性,并考察了pH、液固比和浸出时间等条件对镍渣样中铬、铅、铜和锌等重金属浸出特性的影响。结果表明,镍渣中的重金属总量约为渣样的0.9%,且铬、铜和锌的含量较高,需进行安全管理。实验所用镍渣样品为第Ⅰ类一般工业固体废物。在强酸条件下镍渣中重金属浸出浓度较大,pH3后浸出浓度显著降低;液固比40 L/kg时,镍渣中重金属不断溶出,液固比40 L/kg后,浸出达到饱和,浸出浓度趋于平衡;随着浸出时间的增加,重金属离子的浸出浓度先增加后减少,但由于各重金属性质不同,各重金属达到最大浸出浓度的时间不同。     

Effect of warfare waste on soil: a case study of Gallipoli Peninsula (Turkey)

Gallipoli is a small town on the European side of the Dardanelles Strait, in Turkey. More than 450,000 soldiers gave their lives on the Gallipoli Peninsula (Gallipoli Campaign) over a nine-month period during World War I. In that war, many naval and landing bombs were exploded. The ingredients of these bombs may cause heavy metal contamination in soils. An environmental geochemical investigation has been carried out around Gallipoli Peninsula in order to determine the extent of chemical pollution in the soil. The preliminary data reveal that soils in the area are, in general, not contaminated. The concentrations of many heavy metals, such as arsenic (As), cadmium (Cd), copper (Cu), chromium (Cr), cobalt (Co), manganese (Mn), nickel (Ni), lead (Pb), strontium (Sr), vanadium (V) and zinc (Zn) are in the range of those of average agricultural soils. These low concentrations are explained by the good leaching characteristics of Oligocene–Miocene rocks, Pleistocene terrace material, alluvium sandy-silty soils, and surface run-off.     

含重金属水处理污泥的固化和浸出毒性研究

工业危险固体废物在进行安全填埋前需要进行固化稳定处理。针对电镀厂和皮革厂含重金属的水处理污泥 ,用不同比例的水泥、粉煤灰进行固化稳定处理。考虑酸雨环境 ,浸出实验采用TCLP标准。电镀厂污泥单独固化时 ,其浸出液中铜离子浓度由 78 0mg/L下降到 1 5mg/L ;镍离子浓度由 2 2 4 5mg/L下降到 2 2 2mg/L ,高于危险废物允许进入填埋区 15mg/L的控制限值。电镀厂污泥与皮革厂污泥混合后固化 ,浸出液毒性明显降低。铜离子的浸出浓度降低到1 98mg/L ,镍离子降低到 4 10mg/L ,总铬降低到 0 4 0mg/L ,各项指标均低于国家危险废物允许进入填埋区的控制限值 ,可安全填埋。     

Arsenic leachability and speciation in cement immobilized water treatment sludge

Arsenic leachability and speciation in cement immobilized water treatment sludge were investigated with leaching tests and X-ray absorption near edge structure (XANES) spectroscopy. The As leachability in the sludge determined with the toxicity characteristic leaching procedure (TCLP) and the waste extraction test (WET) was 283 and 7490 microgl(-1), respectively. Extractions with a lower liquid to solid ratio, under anaerobic conditions, and using citric acid buffer solution dramatically increased the leachate As concentration. XANES results showed that the As(III) composition was reduced from 51.1% of the total As content in the sludge to 16.3% in the cement treated sample with 28 days of cure. When the cement treated sample was cured for two years, the As(III) composition was decreased to 7.4%. The cement treatment reduced the As leachability. The leachate As(III) and total As concentrations were of the same order of magnitude in the samples cured for 28 days as for 2yr. However, consistently lower concentrations were detected in samples with longer cure time. The results of this study improve our understanding of arsenic speciation and leachability in the cement matrix after long cure times.     

Evaluation of pressure treated wood impact on landfill waste decomposition using a methane yield assay

Research was conducted to investigate the potential impact of CCA-treated wood and other arsenic-free Cu-based preservative-treated wood on microorganisms, involved in the anaerobic decomposition of waste in landfills. Wood preservatives used included alkaline copper quat (ACQ), copper citrate (CC), copper boron azole (CBA), copper dimethyldithiocarbamate (CDDC), and chromated copper arsenate (CCA). The biochemical methane potential (BMP) assay was used to estimate the possible impacts. The methane yields of mixtures of preservative-treated wood or untreated wood with cellulose (group 1) and these wood samples only (group 2) were determined. An analysis of variance (ANOVA) test found that there were no significant differences among methane yields results in either group 1 or group 2, at the 0.05 level of significance. The results indicate that under the conditions tested, none of the treated wood products evaluated were toxic to the methane-producing organisms. At the end of the assays, test bottle contents were analyzed for Cu, Cr, and As. When the fraction of each metal in the solution (relative to original metal in the wood, leachability %) was examined, As was present at the great extent. The leachability of As was in the range from 15.1% to 21.7% while relatively low leachability (1.7-7.6%) of Cu was observed.     

A Comparison of Two Techniques for the Collection and Analysis of Polynuclear Aromatic Compounds in Ambient Air

A demonstration of the GHEMFIX solidification/stabilization process was conducted under the United States Environmental Protection Agency’s (EPA) Superfund Innovative Technology Evaluation (SITE) program. The demonstration was conducted in March 1989, at the Portable Equipment Salvage Company (PESC) uncontrolled hazardous waste site in Clackamas, Oregon. Waste containing lead, copper, and polychlorinated biphenyls (PCBs) from four different areas of the site were treated. Results showed substantial reduction of leachable lead and copper between the untreated waste and treated waste utilizing the EPA Toxicity Characteristics Leaching Procedure (TCLP) test. The effectiveness of this process for immobilizing PCBs could not be determined since the raw waste did not leach PCBs at high concentrations, utilizing the TCLP test. Data from other leaching tests for lead and copper would need to be utilized as input into a site specific groundwater model to determine whether solidification/stabilization would be an acceptable remedy for the site. Physical testing results indicated durability in exposed conditions.     

Effect of humic substance on thermal treatment of chromium(VI)-containing latosol soil

Latosol soils contaminated with chromium(VI) [Cr(VI)], which is hazardous, can be recycled as raw materials for porcelain and construction sectors if a proper thermal stabilization process is implemented. This study investigates how thermal treatment affects Cr behavior during the sintering of latosol and deorganic latosol samples; both samples are artificially contaminated with CrO3. Approaches including X-ray absorption spectroscopy, scanning electron microscopy, N2-based Brunauer Emmett Teller surface analyzer, thermogravimetric analyzer/differential scanning calorimeter, and the toxicity characteristic leaching procedure promulgated by Taiwan Environmental Protection Administration are used in this study. After drying the Cr(VI)-contaminated latosol (i.e., containing 37,120 mg of Cr/kg sample) at 105 degrees C, approximately 80% of the doped CrO3 is chemically reduced to Cr(OH)3 by a humic substance naturally existing in the soil. In contrast, in the organics-free CrO3-contaminated latosol dried at 105 degrees C, only 9% of the doped CrO3 is reduced to Cr(OH)3. Heating the samples at 500 and 1100 degrees C transforms hazardous Cr(VI) into Cr(III) that is negligibly toxic; Cr2O3, which is insoluble, is detected as the most abundant Cr species. Moreover, formation of Cr2SiOs, which is suggested to relate to low Cr leaching, is only detected in the sample heated at 1100 degrees C. Surface morphology, surface area, and thermogravimetric analyzer/differential scanning calorimeter results demonstrate that thermal treatment at 1100 degrees C can incur considerable soil sintering/ melting if the humic substance in the soil has been heated off previously. Finally, Cr concentrations in the toxicity characteristic leaching procedure leachates collected from the samples thermally treated at 1100 degrees C for 4 hr are < or =0.21 mg of Cr L(-1) that are much less than the Taiwan Environmental Protection Administration regulatory limit (<5 mg of Cr L(-1)); consequently, these two samples are nonhazardous, and they have the potential for resource recycling. Conversely, Cr concentrations in the leachates from all 500 degrees C and 105 degrees C samples are in the 25.6-1279 mg L(-1) range.     

电镀污泥的热处理特性以及对金属回收的影响

焙烧-酸浸法可有效回收电镀污泥中的有价金属,而污泥的热处理特性是决定能否采用焙烧预处理的重要因素。研究了氧化焙烧和还原焙烧对污泥成分和金属浸出性的影响,并对焙烧前后的污泥进行了金属形态分析和X射线衍射(XRD)分析。结果表明,焙烧预处理实现了污泥减量和金属富集;ES1经氧化焙烧后金属浸出率接近原泥,Cu的浸出率达99%;ES2的还原焙烧效果优于氧化焙烧,特别是Cu的浸出率超过97%,XRD分析发现,还原焙烧过程中金属Cu被还原为铁铜合金;2种焙烧均造成了ES3中目标金属Ni的浸出率的降低;金属浸出性的下降与残渣态的形成有关。