Cadmium (Cd) and lead (Pb) in water and soil could be adsorbed by biochar produced from corn straw. Biochar pyrolyzed under 400°C for 2 h could reach the ideal removal efficiencies (99.24%and 98.62% for Cd and Pb, respectively) from water with the biochar dosage of 20 g·L–1 and initial concentration of 20 mg·L–1. The pH value of 4–7 was the optimal range for adsorption reaction. The adsorption mechanism was discussed on the basis of a range of characterizations, including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and Raman analysis; it was concluded as surface complexation with active sorption sites (-OH, -COO-), coordination with π electrons (C = C, C = O) and precipitation with inorganic anions (OH-, CO32–, SO42–) for both Cd and Pb. The sorption isotherms fit Langmuir model better than Freundlich model, and the saturated sorption capacities for Cd and Pb were 38.91 mg·g-1 and 28.99 mg·g–1, respectively. When mixed with soil, biochar could effectively increase alkalinity and reduce bioavailability of heavy metals. Thus, biochar derived from corn straw would be a green material for both removal of heavy metals and amelioration of soil.
Arsanilic acid (ASA), copper ion (Cu2+) and phosphate (PO43–) are widely used as feed additives for pigs. Most of these three supplemented feed additives were excreted in feces and urine. Anaerobic digestion is often used for the management of pig manure. However, the interaction of ASAwith Cu2+ or PO43– on anaerobic digestion is still not clear. In this study, the influence of ASA, Cu2+, PO43– and their interaction on anaerobic digestion of pig manure and the possible mechanisms were investigated. The initial concentrations of ASA, Cu2+ and PO43– were 0.46 mM, 2 mM and 2 mM in the anaerobic digester, respectively. The methanogenesis was severely inhibited in the assays with only ASA addition, only Cu2+ addition and ASA + PO43– addition with the inhibition index of 97.8%, 46.6% and 82.6%, respectively, but the methanogenesis inhibition in the assay with ASA + Cu2+ addition was mitigated with the inhibition index of 39.4%. PO43– had no obvious impacts on the degradation of ASA. However, Cu2+ addition inhibited the degradation of ASA, and mitigated the methanogenesis inhibition. The existence of ASA would inhibit methanogenesis and generate more toxic inorganic arsenic compounds during anaerobic digestion, implying the limitation of anaerobic digestion for ASA- contaminated animal manure. However, the co-existence of ASA and Cu2+ could mitigate the inhibition. These results could provide useful information for the management of anaerobic digestion of pig manure containing ASA and Cu2+.
A spent fluid catalytic cracking (FCC) catalyst containing lanthanum (La) was used as a novel adsorbent for phosphorus (P) in simulated wastewater. The experiments were conducted in a batch system to optimize the operation variables, including pH, calcination temperature, shaking time, solid-liquid ratio, and reaction temperature under three initial P-concentrations (C0 = 0.5, 1.0, and 5.0 mg/L). Orthogonal analysis was used to determine that the initial P-concentration was the most important parameter for P removal. The P-removal rate exceeded 99% and the spent FCC catalyst was more suitable for use in low P-concentration wastewater (C0 <5.0 mg/L). Isotherms, thermodynamics and dynamics of adsorption are used to analyze the mechanism of phosphorus removal. The results show that the adsorption is an endothermic reaction with high affinity and poor reversibility, which indicates a low risk of second releasing of phosphate. Moreover, chemical and physical adsorption coexist in this adsorption process with LaPO4 and KH2PO4 formed on the spent FCC catalyst as the adsorption product. These results demonstrate that the spent FCC catalyst containing La is a potential adsorbent for P-removal from wastewater, which allows recycling of the spent FCC catalyst to improve the quality of water body.
Ambient PM2.5 samples were collected at four sites in Xiamen, including Gulangyu (GLY), Hongwen (HW), Huli (HL) and Jimei (JM) during January, April, July and October 2013. Local source samples were obtained from coal burning power plants, industries, motor vehicles, biomass burning, fugitive dust, and sea salt for the source apportionment studies. The highest value of PM2.5 mass concentration and species related to human activities (SO42–, NO3–, Pb, Ni, V, Cu, Cd, organic carbon (OC) and elemental carbon (EC)) were found in the ambient samples from HL, and the highest and lowest loadings of PM2.5 and its components occurred in winter and summer, respectively. The reconstructed mass balance indicated that ambient PM2.5 consisted of 24% OM (organic matter), 23% sulfate, 14% nitrate, 9% ammonium, 9% geological material, 6% sea salt, 5% EC and 10% others. For the source profiles, the dominant components were OC for coal burning, motor vehicle, biomass burning and sea salt; SO42– for industry; and crustal elements for fugitive dust. Source contributions were calculated using a chemical mass balance (CMB) model based on ambient PM2.5 concentrations and the source profiles. GLY was characterized by high contributions from secondary sulfate and cooking, while HL and JM were most strongly affected by motor vehicle emissions, and biomass burning and fugitive dust, respectively. The CMB results indicated that PM2.5 from Xiamen is composed of 27.4% secondary inorganic components, 20.8% motor vehicle emissions, 11.7% fugitive dust, 9.9% sea salt, 9.3% coal burning, 5.0% biomass burning, 3.1% industry and 6.8% others.
The considerable compounds content, abundance, and low costs involved has led to the proposal to use sewage sludge as raw material for biodiesel production. The transesterification reaction is catalyzed using an acid catalyst instead of base catalysts because of the high free fatty acid concentration. However, the use of a base catalyst, particularly a solid base catalyst, has certain advantages, including faster reaction speed and easier separation. In this study, we utilize in situ transesterification by base catalyst (KOH, KOH/activated carbon (AC) and KOH/CaO) with sewage sludge as raw material. Many conditions have been tested to increase biodiesel yield through single-factor tests, including mass fraction and catalyst dosage. Preliminary experiments have optimized reaction time and temperature. However, the three catalysts did not work better than H2SO4, which had a maximum yield of 4.6% (dry sewage sludge base) considering the purity by KOH, KOH/CaO, and KOH/AC. The features of the catalyst were analyzed using XRD, BETand SEM. As to BETof KOH/AC and the good spiculate formation of KOH crystal appears to be essential to its function. As for KOH/CaO, the formation of K2O and absorption points is likely essential.
The quantification and effects of system pH value on the interactions between Pb(II) and the biopolymer in activated sludge were investigated. The biopolymer had two protein-like fluorescence peaks (Ex/Em = 280 nm/326–338 nm for peak A; Ex/Em = 220–230 nm/324–338 nm for peak B). The fluorescence intensities of peak B were higher than those of peak A. The fluorophores of both peaks could be largely quenched by Pb(II), and the quencher dose for peak B was about half of that for peak A. The modified Stern-Volmer equation well depicted the fluorescence quenching titration. The quenching constant (Ka) values for both peaks decreased with rising system pH value, and then sharply decreased under alkaline conditions. It could be attributed to that the alkaline conditions caused the reduction of available Pb(II) due to the occurrence of Pb(OH)2 sediments. The Ka values of peak B were bigger than those for peak A at the same system pH values. Accordingly, the aromatic proteins (peak B) played a key role in the interactions between metal ions and the biopolymer.
It is common that 2,4,6-trichlorophenol (TCP) coexists with nitrate or nitrite in industrial wastewaters. In this work, simultaneous reductive dechlorination of TCP and denitrification of nitrate or nitrite competed for electron donor, which led to their mutual inhibition. All inhibitions could be relieved to a certain degree by augmenting an organic electron donor, but the impact of the added electron donor was strongest for TCP. For simultaneous reduction of TCP together with nitrate, TCP’s removal rate value increased 75% and 150%, respectively, when added glucose was increased from 0.4 mmol?L–1 to 0.5 mmol?L–1 and to 0.76 mmol?L–1. For comparison, the removal rate for nitrate increased by only 25% and 114% for the same added glucose. The relationship between their initial biodegradation rates versus their initial concentrations could be represented well with the Monod model, which quantified their half-maximum-rate concentration (KS value), and KS values for TCP, nitrate, and nitrite were larger with simultaneous reduction than independent reduction. The increases in KS are further evidence that competition for the electron donor led to mutual inhibition. For bioremediation of wastewater containing TCP and oxidized nitrogen, both reduction reactions should proceed more rapidly if the oxidized nitrogen is nitrite instead of nitrate and if readily biodegradable electron acceptor is augmented.
The objective of this study was to provide insight into human exposure to trace contaminants bearing red mud, derived precipitates and geopolymeric blocks due to inhalation contact and/or hand-to-mouth ingestion. The in vitro bioaccessibility behavior of trace contaminants was investigated with the PBET (physiologically based extraction test), ALF (artificial lysosomal fluid) and MGS (modified Gamble’ solution) methods. The results showed that total contents of trace contaminants and operation parameters, such as pH and chelating properties of simulated gastrointestinal phases (PBET), played a joint role in controlling the bioaccessibility efficacy for size-fractionated red mud particles. As for airborne particles (<38 μm size fractions), trace contaminants concentrations extracted by MGS was significantly higher than those by ALF. Additionally, higher bioaccessibility (PBET) values of Cu, Pb, Zn, As, V and U were obtained from red mud derived precipitates compared with those of red mud itself. Even though short-term and long-term leaching values of trace contaminants were relatively lower in the prepared geopolymeric blocks, the health risk could be significantly higher due to the more pronounced bioaccessibility characteristics.
With extensive use of lithium ion batteries (LIBs), amounts of LIBs were discarded, giving rise to growth of resources demand and environmental risk. In view of wide usage of natural graphite and the high content (12%–21%) of anode graphite in spent LIBs, recycling anode graphite from spent LIBs cannot only alleviate the shortage of natural graphite, but also promote the sustainable development of related industries. After calcined at 600°C for 1 h to remove organic substances, anode graphite was used to prepare graphene by oxidation-reduction method. Effect of pH and N2H4·H2O amount on reduction of graphite oxide were probed. Structure of graphite, graphite oxide and graphene were characterized by XRD, Raman and FTIR. Graphite oxide could be completely reduced to graphene at pH 11 and 0.25 mL N2H4·H2O. Due to the presence of some oxygen-containing groups and structure defects in anode graphite, concentrated H2SO4 and KMnO4 consumptions were 40% and around 28.6% less than graphene preparation from natural graphite, respectively.
We assessed the contamination levels of Mn, Zn, Cr, Cu, Ni, Pb, As and Hg and the risks posed by these potentially harmful elements in top-soils around a municipal solid waste incinerator (MSWI).We collected 20 soil samples, with an average pH of 8.1, and another fly ash sample emitted from the MSWI to investigate the concentrations of these elements in soils. We determined the concentrations of these elements by inductively coupled plasma–optical emission spectrometer (ICP-OES), except for Hg, which we measured by AF-610B atomic fluorescence spectrometer (AFS). We assessed the risks of these elements through the use of geoaccumulation index (Igeo), potential ecological risk index (RI), hazard quotient (HQi) and cancer risk (Riski). The results showed that concentrations of potentially harmful elements in soil were influenced by the wind direction, and the concentrations of most elements were higher in the area northwest of the MSWI, compared with the area southeast of the incinerator, with the exception of As; these results were in accordance with those results acquired from our contour maps. According to the Igeo values, some soil samples were clearly polluted by Hg emissions. However, the health risk assessment indicated that the concentrations of Hg and other elements in soil did not pose non-carcinogenic risks to the local populations. This was also the case for the carcinogenic risks posed by As, Cr, and Ni. The carcinogenic risk posed by As was higher, in the range 6.49 × 10–6–9.58 × 10–6, but this was still considered to be an acceptable level of risk.
Electrochemically active bacteria (EAB) on the cathodes of microbial electrolysis cells (MECs) can remove metals from the catholyte, but the response of these indigenous EAB toward exotic metals has not been examined, particularly from the perspective of the co-presence of Cd(II) and Cr(VI) in a wastewater. Four known indigenous Cd-tolerant EAB of Ochrobactrum sp X1, Pseudomonas sp X3, Pseudomonas delhiensis X5, and Ochrobactrum anthropi X7 removed more Cd(II) and less Cr(VI) in the simultaneous presence of Cd(II) and Cr(VI), compared to the controls with individual Cd(II) or single Cr(VI). Response of these EAB toward exotic Cr(VI) was related to the associated subcellular metal distribution based on the sensing of fluorescence probes. EAB cell membrane harbored more cadmium than chromium and cytoplasm located more chromium than cadmium, among which the imaging of intracelluler Cr(III) ions increased over time, contrary to the decreased trend for Cd(II) ions. Compared to the controls with single Cd(II), exotic Cr(VI) decreased the imaging of Cd(II) ions in the EAB at an initial 2 h and negligibly affected thereafter. However, Cd(II) diminished the imaging of Cr (III) ions in the EAB over time, compared to the controls with individual Cr(VI). Current accelerated the harboring of cadmium at an initial 2 h and directed the accumulation of chromium in EAB over time. This study provides a viable approach for simultaneously quantitatively imaging Cd(II) and Cr (III) ions in EAB and thus gives valuable insights into the response of indigenous Cd-tolerant EAB toward exotic Cr(VI) in MECs.
Earthworm heavy metal concentrations (critical body residues, CBRs) may be the most relevant measures of heavy metal bioavailability in soils and may be linkable to toxic effects in order to better assess soil ecotoxicity. However, as earthworms possess physiological mechanisms to secrete and/or sequester absorbed metals as toxicologically inactive forms, total earthworm metal concentrations may not relate well with toxicity.
Objective
The objectives of this research were to: i) develop LD50s (total earthworm metal concentration associated with 50% mortality) for Cd, Pb, and Zn; ii) evaluate the LD50 for Zn in a lethal Zn-smelter soil; iii) evaluate the lethal mixture toxicity of Cd, Pb, and Zn using earthworm metal concentrations and the toxic unit (TU) approach; and iv) evaluate total and fractionated earthworm concentrations as indicators of sublethal exposure.
Methods
Earthworms (Eisenia fetida (Savigny)) were exposed to artificial soils spiked with Cd, Pb, Zn, and a Cd?Pb?Zn equitoxic mixture to estimate lethal CBRs and mixture toxicity. To evaluate the CBR developed for Zn, earthworms were also exposed to Zn-contaminated field soils receiving three different remediation treatments. Earthworm metal concentrations were measured using a procedure devised to isolate toxicologically active metal burdens via separation into cytosolic and pellet fractions.
Results and Discussion
Lethal CBRs inducing 50% mortality (LD50, 95% CI) were calculated to be 5.72 (3.54–7.91), 3.33 (2.97–3.69), and 8.19 (4.78–11.6) mmol/kg for Cd, Pb, and Zn, respectively. Zn concentrations of dead earthworms exposed to a lethal remediated Zn-smelter soil were 3-fold above the LD50 for Zn and comparable to earthworm concentrations in lethal Zn-spiked artificial soils, despite a 14-fold difference in total soil Zn concentration between lethal field and artificial soils. An evaluation of the acute mixture toxicity of Cd, Pb, and Zn in artificial soils using the Toxic Unit (TU) approach revealed an LD50 (95% CI) of 0.99 (0.57–1.41) TU, indicating additive toxicity.
Conclusions
Total Cd, Pb, and Zn concentrations in earthworms were good indicators of lethal metal exposure, and enabled the calculation of LD50s for lethality. The Zn-LD50 developed in artificial soil was applicable to earthworms exposed to remediated Zn-smelter soil, despite a 14-fold difference in total soil Zn concentrations. Mixture toxicity evaluated using LD50s from each single metal test indicated additive mixture toxicity among Cd, Pb, and Zn. Fractionation of earthworm tissues into cytosolic and pellet digesis yielded mixed results for detecting differences in exposure at the sublethal level.
Recommendation and Outlook
CBRs are useful in describing acute Cd, Pb, and Zn toxicity in earthworms, but linking sublethal exposure to total and/or fractionated residues may be more difficult. More research on detoxification, regulation, and tissue and subcellular partitioning of heavy metals in earthworms and other invertebrates is needed to establish the link between body residue and sublethal exposure and toxicity.
Exploration of heavy metals and organic pollutants, their leaching capacity along with health and environmental risks in contaminated industrial construction and demolition waste (ICDW) within a pesticide manufacturing plant were investigated. A maximum content of 90.8 mg?kg–1 Cd was found present in the wastes, which might originate from phosphorus rocks and industrial sulfuric acid used in pesticide production processes. An average concentration of 979.8 mg?kg–1 dichlorovos and other 11 organophosphorus pesticide were also detected. Relatively high leaching rates of around 4.14‰were obtained from laboratory simulated ICDW using both glacial acetic acid-sodium hydroxide and deionized water. Pesticide pollutants had the strongest tendency to retaining on dry bricks (leaching rate 1.68‰) compared to mortar-coatings, etc. due to their different physical characteristics and octanol-water partioning coefficient. Mobility of pesticide from on-site ICDW by water was spatially correlated to waste types, process sections and human activities, with a flux of leaching rate between 5.9‰ to 27.4%. Risk-based corrective action (RBCA) model was used to simulate the risk of contaminated ICDW debris randomly scattered. Oral and dermal ingestion amount by local workers was 9.8 × 10–3 and 1.9 × 10–2 mg?(kg?d)–1, respectively. Potential leaching risk to aquatic systems exceeded the limit for nearly 75% waste. Environmental and health risk exceedance was found in most ICDW, while the risk value of the most severely contaminated brick waste was 660 times beyond critical level. Implications for waste management involving construction and deconstruction work, waste transferring and regulation supplying were also provided.
Copper recovery is the core of waste printed circuit boards (WPCBs) treatment. In this study, we proposed a feasible and efficient way to recover copper from WPCBs concentrated metal scraps by direct electrolysis and factors that affect copper recovery rate and purity, mainly CuSO4·5H2O concentration, NaCl concentration, H2SO4 concentration and current density, were discussed in detail. The results indicated that copper recovery rate increased first with the increase of CuSO4·5H2O, NaCl, H2SO4 and current density and then decreased with further increasing these conditions. NaCl, H2SO4 and current density also showed a similar impact on copper purity, which also increased first and then decreased. Copper purity increased with the increase of CuSO4·5H2O. When the concentration of CuSO4·5H2O, NaCl and H2SO4 was respectively 90, 40 and 118 g/L and current density was 80 mA/cm2, copper recovery rate and purity was up to 97.32% and 99.86%, respectively. Thus, electrolysis proposes a feasible and prospective approach for waste printed circuit boards recycle, even for e-waste, though more researches are needed for industrial application.
In this study, FeVO4 was prepared and used as Fenton-like catalyst to degrade orange G (OG) dye. The removal of OG in an aqueous solution containing 0.5 g·L–1 FeVO4 and 15 mmol·L–1 hydrogen peroxide at pH 7.0 reached 93.2%. Similar rates were achieved at pH 5.7 (k = 0.0471 min–1), pH 7.0 (k = 0.0438 min–1), and pH 7.7 (k = 0.0434 min–1). The FeVO4 catalyst successfully overcomes the problem faced in the heterogeneous Fenton process, i.e., the narrow working pH range. The data for the removal of OG in FeVO4 systems containing H2O2 conform to the Langmuir–Hinshelwood model (R2 = 0.9988), indicating that adsorption and surface reaction are the two basic mechanisms for OG removal in the FeVO4–H2O2 system. Furthermore, the irradiation of FeVO4 by visible light significantly increases the degradation rate of OG, which is attributed to the enhanced rates of the iron cycles and vanadium cycles.
With the increasing concern about the serious global energy crisis and high energy consumption during high content solid wastes (HCSWs) treatment, microbial fuel cell (MFC) has been recognized as a promising resource utilization approach for HCSW stabilization with simultaneous electrical energy recovery. In contrast to the conventional HCSW stabilization processes, MFC has its unique advantages such as direct bio-energy conversion in a single step and mild reaction conditions (viz., ambient temperature, normal pressure, and neutral pH). This review mainly introduces some important aspects of electricity generation from HCSWand its stabilization in MFC, focusing on: (1) MFCs with different fundamentals and configurations designed and constructed to produce electricity from HCSW; (2) performance of wastes degradation and electricity generation; (3) prospect and deficiency posed by MFCs with HCSWas substrates. To date, the major drawback of MFCs fueled by HCSW is the lower power output than those using simple substrates. HCSW hydrolysis and decomposition would be a major tool to improve the performance of MFCs. The optimization of parameters is needed to push the progress of MFCs with HCSW as fuel.
Waste pickling liquors (WPLs) containing high concentrations of iron and acid are hazardous waste products from the steel pickling processes. A novel combined coprecipitation–oxidation method for iron recovery by Fe3O4 nanoparticle production from the WPLs was developed in this study. An oxidation–reduction potential monitoring method was developed for real-time control of the Fe2+/Fe3+ molar ratio. The key coprecipitation–oxidation parameters were determined using the orthogonal experimental design method. The use of promoters greatly improved the Fe3O4 nanoparticle crystallinity, size, magnetization, and dispersion. X-ray diffraction patterns showed that the produced Fe3O4 nanoparticles were single phase. The Fe3O4 nanoparticles were approximately spherical and slightly agglomerated. Vibrating sample magnetometry showed that the Fe3O4 nanoparticles produced from the WPLs had good magnetic properties, with a saturation magnetization of 80.206 emu·g–1 and a remanence of 10.500 emu·g–1. The results show that this novel coprecipitation–oxidation method has great potential for recycling iron in WPLs.
Direct individual analysis using Scanning Electron Microscopy combined with online observation was conducted to examine the S-rich particles in PM2.5 of two typical polluted haze episodes in summer and winter from 2014 to 2015 in Beijing. Four major types of S-rich particles, including secondary CaSO4 particles (mainly observed in summer), S-rich mineral particles (SRM), S-rich water droplets (SRW) and (C, O, S)-rich particles (COS) were identified.We found the different typical morphologies and element distributions of S-rich particles and considered that (C, O, S)-rich particles had two major mixing states in different seasons. On the basis of the S-rich particles’ relative abundances, S concentrations and their relationships with PM2.5 as well as the seasonal comparison, we revealed that the S-participated formation degrees of SRM and SRW would enhance with increasing PM2.5 concentration. Moreover, C-rich matter and sulfate had seasonally different but significant impacts on the formation of COS.
Nitrogen (N) and phosphorus (P) released from the sediment to the surface water is a major source of water quality impairment. Therefore, inhibiting sediment nutrient release seems necessary. In this study, red soil (RS) was employed to control the nutrients released from a black-odorous river sediment under flow conditions. The N and P that were released were effectively controlled by RS capping. Continuous-flow incubations showed that the reduction efficiencies of total N (TN), ammonium (NH4+-N), total P (TP) and soluble reactive P (SRP) of the overlying water by RS capping were 77%, 63%, 77% and 92%, respectively, and nitrification and denitrification occurred concurrently in the RS system. An increase in the water velocity coincided with a decrease in the nutrient release rate as a result of intensive water aeration.
The REDEQL.EPAK computer model was used to study speciation of Pb, Cd, Zn, and Ca in leachates from dolomitic Pb mine tailings. By allowing or disallowing precipitation of solids and equilibration of the modelled leachate with atmospheric C02, comparison of fresh and aged leachates was made. The effects of treatment of the tailings with phosphate containing fertilizer were studied through addition of P043– to the modelled solution. Equilibrium constants pertaining to metal ion-humic acid complexation were added to the thermodynamic data base of the model in order to study the effects of decaying plant material on tailings leachate.Initial leachate of the tailings is found to be supersaturated with Cd and Zn. Non-complexed (free) Cd2+ and Zn2+ is predicted to comprise most of the soluble form of these metals in the leachate; Pb is predicted to be present largely as PbCO3 ion pair. Equilibration of the leachate with the atmosphere is predicted to lead to extensive precipitation of CdCO3 and ZnSiO3. Precipitation of Pb5(PO4)3Cl is predicted at high PO43– concentration and at low pH. Complexation by the humic acid is predicted to compete effectively with other ligands in the leachate for the metal ions. The results are compared with experimental findings. 相似文献
