Volatile organic compounds and metal leaching from composite products made from fiberglass-resin portion of printed circuit board waste

This study focused on the volatile organic compounds (VOCs) and metal leaching from three kinds of composite products made from fiberglass-resin portion (FRP) of crushed printed circuit board (PCB) waste, including phenolic molding compound (PMC), wood plastic composite (WPC), and nonmetallic plate (NMP). Released VOCs from the composite products were quantified by air sampling on adsorbent followed by thermal desorption and GC-MS analysis. The results showed that VOCs emitted from composite products originated from the added organic components during manufacturing process. Phenol in PMC panels came primarily from phenolic resin, and the airborne concentration of phenol emitted from PMC product was 59.4 ± 6.1 μg/m(3), which was lower than odor threshold of 100% response for phenol (180 μg/m(3)). VOCs from WPC product mainly originated from wood flour, e.g., benzaldehyde, octanal, and d-limonene were emitted in relatively low concentrations. For VOCs emitted from NMP product, the airborne concentration of styrene was the highest (633 ± 67 μg/m(3)). Leaching characteristics of metal ions from composite products were tested using acetic acid buffer solution and sulphuric acid and nitric acid solution. Then the metal concentrations in the leachates were tested by ICP-AES. The results showed that only the concentration of Cu (average = 893 mg/L; limit = 100 mg/L) in the leachate solution of the FRP using acetic acid buffer solution exceeded the standard limit. However, concentrations of other metal ions (Pb, Cd, Cr, Ba, and Ni) were within the standard limit. All the results indicated that the FRP in composite products was not a major concern in terms of environmental assessment based upon VOCs tests and leaching characteristics.     

Isotopic tracing of landfill leachates and pollutant lead mobility in soil and groundwater

Here we provide evidence of the capability of stable lead isotopes to trace landfill leachate in a shallow groundwater. The municipal landfill we have investigated is located in southeastern France. It has no bottom liner, and wastes are placed directly on the ground. Stable lead isotopes allow the characterization of this landfill leachate signature (206Pb/207Pb = 1.189 +/- 0.004) that is clearly different from that of the local atmosphere (206Pb/207Pb = 1.150 +/- 0.006) and crustal lead (206Pb/207Pb = 1.200 +/- 0.005). Piezometers located in the direct vicinity of the landfill generally display this contaminant imprint. The landfill plume is monitored up to 1000 m downgradient of the landfill, in very good agreement with evaluation from chloride concentration. Meanwhile, 206Pb/207Pb ratios measured at a piezometer located 4600 m downgradient of the landfill suggest a contamination by the landfill plume. This result shows that the complexity of a pollutant plume dispersion in this shallow groundwater system requires several independent tracers to clearly resolve origin and transport pathways for contaminants. Furthermore, seasonal rainfall variation for this Mediterranean mixed Quaternary alluvion reservoir and the use of KCl fertilizers might favor an efficient remobilization of atmospheric lead in plowed soils and its transfer into groundwater as shown by lead isotope systematics.     

Comparison of Cd(II), Cu(II), and Pb(II) biouptake by green algae in the presence of humic acid

The present study examines the role of humic acid, as a representative of dissolved organic matter, in Cd(II), Cu(II), and Pb(II) speciation and biouptake by green microalgae. Cellular and intracellular metal fractions were compared in the presence of citric and humic acids. The results demonstrated that Cd and Cu uptake in the presence of 10 mg L(-1) humic acid was consistent with that predicted from measured free metal concentrations, while Pb biouptake was higher. By comparing Cd, Cu, and Pb cellular concentrations in the absence and presence of humic acid, it was found that the influence of the increased negative algal surface charge, resulting from humic acid adsorption, on cellular metal was negligible. Moreover, the experimental results for all three metals were in good agreement with the ternary complex hypothesis. Given that metal has much higher affinity with algal sites than humic acid adsorbed to algae, the contribution of the ternary complex to metal bioavailability was negligible in the case of Cd (II) and Cu (II). In contrast, the ternary complex contributed to over 90% of total cellular metal for Pb(II), due to the comparable affinity of Pb to algal sites in comparison with humic acid adsorbed to algae. Therefore, the extension of the biotic ligand model by including the formation of the ternary complex between the metal, humic acid, and algal surface would help to avoid underestimation of Pb biouptake in the presence of humic substances by green algae Chlorella kesslerii.     

Role of transition metals,Fe(II), Cr(II), Pb(II), and Cd(II) in lipid peroxidation

Cod liver oil was oxidized with Fenton-like systems containing transition metals Fe(II), Cr(II), Pb(II), and Cd(II). Malonaldehyde (MA) formed from 10 μl cod liver oil oxidized by a Fenton-like system containing each metal at levels of 0.25, 0.5, 1 and 4 μmol was analyzed by a gas chromatograph equipped with a nitrogen phosphorus detector. The MA production exhibited dose response and the greatest amount (837.0 ± 19.1 nmol) was obtained by the Fe(II) system at the level of l μmol. Generally, higher MA formation is observed in the lower the third ionization potential of the metal. The decreasing order of MA formed in the metal systems at the level of 1 μmol is Fe(II) > Cr(II)(274.1 ± 20.1 nmol) > Pb(II)(150.7 ± 13.0 nmol) > Cd(II)(95.4 ± 6.7 nmol). The amounts of MA formed in Cr(II), Pb(II), and Cd(II) systems were considerably lower than those in the Fe(II) system. The relative formations of MA in the Cr(II) and Pb(II) systems were similar to those in the Fe(II) system. The results suggest that trace amounts of metals contribute oxidative effects to lipid peroxidation followed by various diseases.     

Determination of Cd (II), Cu (II), and Pb (II) in Some Foods by FAAS after Preconcentration on Modified Silica Gels with Thiourea

Abstract: This study describes preconcentration method for determination of Cd (II), Cu (II), and Pb (II) in some food samples. Silica gel was modified with thiourea and characterized by IR and C, H, N, S elemental analysis. Modified silica gel was used as a solid phase extraction for determination of Cd (II), Cu (II) and Pb (II) in tuna fish, biscuit, black tea, rice, ka?ar cheese, honey, tomato paste, and margarine samples. The analytical conditions including eluent type, pH of sample solutions, flow rates of sample and eluent solutions, etc. were optimized. The influence of the matrix ions on the involvement of the Cd (II), Cu (II), and Pb (II) were also studied. GBW 07605 tea standard reference material was used for validation of method. The method was successfully applied for the determination of Cd (II), Cu (II), and Pb (II) ions in food samples. The detection limits were in the range of 0.81 μg/L, 0.38 μg/L, and 0.57 μg/L for cadmium, copper and lead, respectively. The relative standard deviations of the procedure were below 10%. The sorption capacities were found as 92 μmol/L Cd (II), 286 μmol/L Cu (II), and 121 μmol/L Pb (II).     

Leaching of lead from computer printed wire boards and cathode ray tubes by municipal solid waste landfill leachates

The proper management of discarded electronic devices (E-waste) is an important issue for solid waste professionals because of the magnitude of the waste stream and because these devices often contain a variety of toxic metals (e.g., lead). While recycling of E-waste is developing, much of this waste stream is disposed in landfills. Leaching tests are frequently used to characterize the potential of a solid waste to leach when disposed in a landfill. In the United States, the Toxicity Characteristic Leaching Procedure (TCLP) is used to determine whether a solid waste is a hazardous waste by the toxicity characteristic. The TCLP is designed to simulate worse-case leaching in a landfill environment where the waste is co-disposed with municipal solid waste (MSW). While the TCLP is a required analysis from a regulatory perspective, the leachate concentrations measured may not accurately reflect the concentrations observed under typical landfill conditions. Another method that can be performed to assess the degree a pollutant might leach from a waste in a landfill is to use actual landfill leachate as the leaching solution. In this study, two lead-containing components found in electronic devices (printed wire boards from computers and cathode ray tubes from computers and televisions) were leached using the TCLP and leachates from 11 Florida landfills. California's Waste Extraction Test (WET) and the Synthetic Precipitation Leaching Procedure were also performed. The results indicated that the extractions using MSW landfill leachates resulted in lower lead concentrations than those by the TCLP. The pH of the leaching solution and the ability of the organic acids in the TCLP and WET to complex with the lead are factors that regulate the amount of lead leached.     

Chromium release from waste incineration air-pollution-control residues

Cr release overtime was investigated in batch experiments for eleven air-pollution-control residues from eight different municipal solid waste incinerators covering all majorflue gas cleaning technologies. Cr released during 168 h of contact with water showed significant variations among the residues studied. Also for the individual residue, large variations were observed depending on the liquid-to-solid ratio used in the leaching test and the degree of carbonation. It is argued that Al(0) present in the residues can control Cr leaching by reducing Cr(VI) released from the solid phase by dissolution and that exposure to oxygen-either prior to or during the leaching test-depletes the reduction capacity of Al(0) leading to increased Cr leaching. A dynamic model is shown to describe Cr release from all investigated residues by accounting for Al(0) oxidation with Cr(VI), O2, and water as well as Cr(VI) dissolution. The paper reveals that Al-O2-Cr(VI) interactions must be considered very carefully when interpreting Cr leaching data.     

Photochemical coupling reactions between Fe(III)/Fe(II), Cr(VI)/Cr(III), and polycarboxylates: inhibitory effect of Cr species

The roles of chromium species on photochemical cycling of iron and mineralization of polycarboxylates are examined in the presence of Cr(VI) or Cr(III) at pH 2.2-4.0. Under UV irradiation, Cr(III) altered the redox equilibrium of iron species, leading to the shift of the photosteady state toward Fe(II). After a longer time of illumination, total organic carbon (TOC) approached a steady state in the presence of Cr(III) or Cr(VI), whereas oxalate was thoroughly mineralized in the absence of Cr species. The TOC of steady state was closely related to the kind of polycarboxylates, Cr species dosages, pH and O2 atmosphere, but hardly affected by more addition of Fe(III). ESI-MS data indicates that several Cr-oxalate complexes formed in the photochemical reactions, which are responsible for protecting oxalate against further oxidation. A mechanism is proposed for the inhibitory effect of Cr species on oxidation of oxalate and Fe(II). The present study may provide a new insight into the dual environmental effects induced by Cr contaminants especially at heavily chromium-contaminated and dissolved organic matter (DOM)-rich sites.     

Visible light Cr(VI) reduction and organic chemical oxidation by TiO2 photocatalysis

Here we report the simultaneous Cr(VI) reduction and 4-chlorophenol (4-CP) oxidation in water under visible light (wavelength > 400 nm) using commercial Degussa P25 TiO2. This remarkable observation was attributed to a synergistic effect among TiO2, Cr(VI), and 4-CP. It is well known that TiO2 alone cannot remove either 4-CP or Cr(VI) efficiently under visible light. Moreover, the interaction between Cr(VI) and 4-CP is minimal if not negligible. However, we found that the combination of TiO2, Cr(VI), and 4-CP together can enable efficient Cr(VI) reduction and 4-CP oxidation under visible light. The specific roles of the three ingredients in the synergistic system were studied parametrically. It was found that optimal concentrations of Cr(VI) and TiO2 exist for the Cr(VI) reduction and 4-CP oxidation. Cr(VI) was compared experimentally with other metals such as Cu(ll), Fe(lll), Mn(IV), Ce(IV), and V(V). Among all these metal ions, only Cr(VI) promotes the photocatalytic oxidation of 4-CP. The amount of 4-CP removed was directly related to the initial concentration of Cr(VI). The system was also tested with four other chemicals (aniline, salicylic acid, formic acid, and diethyl phosphoramidate). We found that the same phenomenon occurred for organics containing acid and/or phenolic groups. Cr(VI) was reduced at the same time as the organic chemicals being oxidized during photoreaction under visible light. The synergistic effect was also found with pure anatase TiO2 and rutile TiO2. This study demonstrates a possible economical way for environmental cleanup under visible light.     

The physicochemical characterization,equilibrium, and kinetics of heavy metal ions adsorption from aqueous solution by arrowhead plant (Sagittaria trifolia L.) stalk

The arrowhead plant stalk (APS) has been investigated as a novel biosorbent for removal of Cd(II), Pb(II), and Cr(III) ions from aqueous solution. The surface physicochemical properties favorable for metals adsorption were systematically characterized. The Langmuir isotherm fitted well with Cd(II) and Pb(II) adsorption process onto APS while Dubinin–Radushkevich model best described Cr(III) sorption. The maximal adsorption capacities of APS for Cd(II), Pb(II), and Cr(III) were up to 38.2, 97.1, and 23.5 mg·g^?1, respectively. The adsorption kinetic data of individual metal fitted the pseudo‐second order model best. The adsorption of Cd(II) was exothermic, whereas the Pb(II) and Cr(III) underwent endothermic reaction. Overall, this investigation indicated, for the first time, APS is a potentially efficient biosorbent applied in Cd(II), Pb(II), and Cr(III) adsorption. It is also helpful for further utilizing the abundant quantity of APS which were abandoned in dietary arrowhead processing.

Practical applications

The growing food industry around world generates large quantity of by‐products. The high value‐added utilization of food processing by‐products is one of the most important area in food industry. An attempt was made in present study to use the food by‐product, arrowhead plant stalk (APS), as a novel biosorbent for removing Cd(II), Pb(II), and Cr(III) ions. In present study, it was evidenced that the adsorption capacities of APS for Cd(II), Pb(II), and Cr(III) were obviously higher than those of most reported agricultural by‐products. This finding is significant for sustainable utilization of food crop arrowhead plant and elimination of environmental issues arising from the abandoned arrowhead plant stalk.     

Inhibited Cr(VI) reduction by aqueous Fe(II) under hyperalkaline conditions

This study investigated Cr(VI) reduction by dissolved Fe(II) in hyperalkaline pH conditions as found in fluid wastes associated with the U.S. nuclear weapons program. The results show that Cr(VI) reduction by Fe(II) at alkaline pH solutions proceeds very quickly. The amount of Cr(VI) removed from solution and the amount reduced increases with Fe(II):Cr(VI) ratio. However, the Cr(VI) reduction under alkaline pH condition is nonstoichiometric, probably due to Fe(II) precipitation and mixed iron(III)-chromium-(III) (oxy)hydroxides blocking Fe(II) surface sites, as well as removing Fe(II) from solution through O2 oxidation. After Cr(VI) was reduced to Cr(III), it precipitated out as mixed Fe(x)Cr1-xO3(solids) and various Fe(III) precipitates with an overall Cr:Fe ratio of 1:3; all Cr remaining in the solution phase was unreduced Cr(VI). EXAFS data showed that Cr-O and Cr-Cr distances in the precipitates equal to 1.98 and 3.01 A, respectively, consistent with the spinel-type structure as chromite.     

Characterization and preliminary assessment of a sorbent produced by accelerated mineral carbonation

This study shows that calcium silicate/aluminate-based materials can be carbonated to produce sorbents for metal removal. The material chosen for investigation, cement clinker, was accelerated carbonated, and its structural properties were investigated using X-ray diffraction (XRD), scanning electron microscopy, thermal gravimetric and differential thermal analysis, nuclear magnetic resonance spectroscopy, and nitrogen gas adsorption techniques. The principal carbonation reactions involved the transformation of dicalcium silicate, tricalcium silicate, and tricalcium aluminate into a Ca/Al-modified amorphous silica and calcium carbonate. It was found that carbonated cement had high acid buffering capacity, and maintained its structural integrity within a wide pH range. The uptake of Pb(II), Cd(II), Zn(II), Ni(II), Cr(II), Sr(II), Mo(VI), Cs(II), Co(II), and Cu(II) from concentrated (1000 mg L(-1)) single-metal solutions varied from 35 to 170 mg g(-1) of the carbonate cement. The removal of metals was hardly effected by the initial solution pH due to the buffering capability of the carbonated material. The kinetics of Pb, Cd, Cr, Sr, Cs, and Co removal followed a pseudo-second-order kinetic model, whereas the equilibrium batch data for Cu fitted the pseudo-first-order rate equation. PHREEQC simulation supported by XRD analysis suggested the formation of metal carbonates and silicates, calcium molybdate, and chromium (hydro)oxide. Cesium was likely to be adsorbed by Ca/Al-modified amorphous silica.     

Relative leaching and aquatic toxicity of pressure-treated wood products using batch leaching tests

Size-reduced samples of southern yellow pine dimensional lumber, each treated with one of five different waterborne chemical preservatives, were leached using 18-h batch leaching tests. The wood preservatives included chromated copper arsenate (CCA), alkaline copper quaternary, copper boron azole, copper citrate, and copper dimethyldithiocarbamate. An unpreserved wood sample was tested as well. The batch leaching tests followed methodology prescribed in the U.S. Environmental Protection Agency toxicity characteristic leaching procedure (TCLP). The wood samples were first size-reduced and then leached using four different leaching solutions (synthetic landfill leachate, synthetic rainwater, deionized water, and synthetic seawater). CCA-treated wood leached greater concentrations of arsenic and copper relative to chromium, with copper leaching more with the TCLP and synthetic seawater. Copper leached at greater concentrations from the arsenic-free preservatives relative to CCA. Arsenic leached from CCA-treated wood at concentrations above the U.S. federal toxicity characteristic limit (5 mg/L). All of the arsenic-free alternatives displayed a greater degree of aquatic toxicity compared to CCA. Invertebrate and algal assays were more sensitive than Microtox. Examination of the relative leaching of the preservative compounds indicated that the arsenic-free preservatives were advantageous over CCA with respect to waste disposal and soil contamination issues but potentially posed a greater risk to aquatic ecosystems.     

长沙烟区烟叶重金属含量与土壤重金属含量及其性质的相关性分析

为了解长沙烟区烟叶重金属含量与土壤重金属含量及土壤性质的关联规律,采用盆栽试验研究了该区域不同性质土壤烟叶中镉（Cd）、铅（Pb）、汞（Hg）、砷（As）及铬（Cr）的含量,并对烟叶中的重金属含量与对应的土壤中重金属含量及土壤理化性质进行了相关性分析。结果表明:烟叶中重金属富集系数Cd & gt; Hg & gt; Pb & gt; Cr & gt; As,表明烟叶是易富集Cd的作物;烟叶中Cd含量与土壤pH值和有机质含量呈显著负相关性,与速效磷呈显著正相关性;烟叶中Pb含量与土壤有机质含量呈极显著负相关性,与土壤CEC呈显著负相关性;烟叶中Cr含量与土壤有机质含量呈极显著负相关性;烟叶中As含量与土壤中速效磷呈极显著负相关性;烟叶中Cr、Cd和Pb含量分别与土壤中Cr、Cd和Pb存在显著正相关性。      

Simultaneous application of dissolution/precipitation and surface complexation/surface precipitation modeling to contaminant leaching

This paper discusses the modeling of anion and cation leaching from complex matrixes such as weathered steel slag. The novelty of the method is its simultaneous application of the theoretical models for solubility, competitive sorption, and surface precipitation phenomena to a complex system. Selective chemical extractions, pH dependent leaching experiments, and geochemical modeling were used to investigate the thermodynamic equilibrium of 12 ions (As, Ca, Cr, Ba, SO4, Mg, Cd, Cu, Mo, Pb, V, and Zn) with aqueous complexes, soluble solids, and sorptive surfaces in the presence of 12 background analytes (Al, Cl, Co, Fe, K, Mn, Na, Ni, Hg, NO3, CO3, and Ba). Modeling results show that surface complexation and surface precipitation reactions limit the aqueous concentrations of Cd, Zn, and Pb in an environment where Ca, Mg, Si, and CO3 dissolve from soluble solids and compete for sorption sites. The leaching of SO4, Cr, As, Si, Ca, and Mg appears to be controlled by corresponding soluble solids.     

Field-flow fractionation-inductively coupled plasma mass spectrometry: an alternative approach to investigate metal-humic substances interaction

Interaction between metal ions and humic matter was investigated using a hyphenated technique, field-flow fractionation-inductively coupled plasma mass spectrometry (FFF-ICP-MS). Aggregation of a metal-spiked commercial Aldrich humic acid in an aqueous solution of calcium ion or in seawater was examined over time intervals of 0-4320 min. The aggregation was demonstrated by shifts in peak maximum of humic matter from smaller size (2.9 nm) to larger size (5.1 or 5.8 nm in Ca2+ solution or in seawater, respectively) and also by the broadening of size distribution profiles. With FFF, size distribution of humic aggregate was characterized. Further, dominant particle size (2.9 nm), mean particle size (3.8 nm), and diffusion coefficient (1.51 x 10(-6) cm2/s) of humic acid solution were determined. With FFF-ICP-MS, associations of Cd, Cu, and Pb with humic aggregates were examined. The mean diameters of Cd-, Cu-, and Pb-bound humic aggregates in the metal-spiked humic acid were 4.1, 4.5, and 5.8 nm, respectively. These diameters were shifted to 6.0, 6.0, and 6.9 nm, respectively, in the humic acid incubated with calcium solution, whereas they were shifted to 6.5, 5.7, and 7.4 nm, respectively, in the humic acid incubated with seawater for three days. Humic aggregate of small size showed more affinity for Cu than Cd and Pb, whereas the large aggregate showed more affinity for Pb than Cd and Cu, respectively.     

<Emphasis Type="SmallCaps">l</Emphasis>-Cysteine Functionalized Silica Gel as an Efficient Adsorbent for the Determination of Heavy Metals in Foods by ICP-MS

A novel l-cysteine functionalized silica gel adsorbent (SG-Cys) was successfully synthesized and characterized by Fourier transform infrared (FTIR) spectra and elemental analysis. An efficient method for simultaneous determination of heavy metals [V (V), Cr (VI), Cu (II), As (V), Cd (II), and Pb (II)] was developed by inductively coupled plasma-mass spectrometry (ICP-MS) coupled with pre-concentration with the prepared SG-Cys adsorbent. The experimental parameters, including the solution pH, sample flow rate, eluent volume, eluent type, and concentration, have been systematically optimized to obtain higher enrichment factors of target ions. Under the optimum conditions, the enrichment factors of V (V), Cr (VI), Cu (II), As (V), Cd (II), and Pb (II) reached 123, 100, 86, 106, 97, and 94, respectively, and the detection limits were as low as 1.8–3.7 ng L^?1. The proposed method has been applied to the determination of trace heavy metals in water, rice, wheat, corn, and tea samples, which exhibited a satisfactory recovery in the range of 90.6–106.0 %.     

Efficient removal of heavy metal ions with biopolymer template synthesized mesoporous titania beads of hundreds of micrometers size

We demonstrated that mesoporous titania beads of uniform size (about 450 μm) and high surface area could be synthesized via an alginate biopolymer template method. These mesoporous titania beads could efficiently remove Cr(VI), Cd(II), Cr(III), Cu(II), and Co(II) ions from simulated wastewater with a facile subsequent solid-liquid separation because of their large sizes. We chose Cr(VI) removal as the case study and found that each gram of these titania beads could remove 6.7 mg of Cr(VI) from simulated wastewater containing 8.0 mg·L(-1) of Cr(VI) at pH = 2.0. The Cr(VI) removal process was found to obey the Langmuir adsorption model and its kinetics followed pseudo-second-order rate equation. The Cr(VI) removal mechanism of titania beads might be attributed to the electrostatic adsorption of Cr(VI) ions in the form of negatively charged HCrO(4)(-) by positively charged TiO(2) beads, accompanying partial reduction of Cr(VI) to Cr(III) by the reductive surface hydroxyl groups on the titania beads. The used titania beads could be recovered with 0.1 mol·L(-1) of NaOH solution. This study provides a promising micro/nanostructured adsorbent with easy solid-liquid separation property for heavy metal ions removal.     

Analysis of Trace Metals and Perfluorinated Compounds in 43 Representative Tea Products from South China

Six trace metals (Cd, Pb, Cr, Cu, Zn, and Mn) and 2 perfluorinated compounds (PFCs), perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), were analyzed in 43 representative tea products (including 18 green, 12 Oolong, and 13 black teas) from 7 main tea production provinces in China, using the atomic absorption spectrophotometer for trace metals analysis and HPLC‐MS/MS for PFOS and PFOA analysis. The average contents of the 3 essential metals Mn, Cu, and Zn ions in the tea samples were 629.74, 17.75, and 37.38 mg/kg, whereas 3 toxic metals Cd, Cr, and Pb were 0.65, 1.02, and 1.92 mg/kg, respectively. The contents of heavy metals in the 3 types of tea were in the order of black tea > Oolong tea > green tea. Both PFOS and PFOA contents were low and PFOA content was higher than PFOS in the tea samples. The highest concentration of PFOA was 0.25 ng/g dry weight found in a Hunan green tea. The Principal component analysis was performed with the trace metals and PFCs to analyze the relationships of these indices. The results showed that black teas had higher trace metals and PFCs than green and Oolong teas, and the teas from Hunan and Zhejiang provinces had higher Pb and Cr than others.