Facile synthesis of Pd nanoparticles on SiO2 for hydrogenation of biomass-derived furfural

This report shows that furfuryl alcohol can be selectively produced from the hydrogenation of furfural using supported Pd nanoparticles. Furfuryl alcohol is widely used as solvent and chemical intermediate for the synthesis of fine chemicals. Here, various Pd nanoparticles supported on mesoporous SiO₂ (Pd/SiO₂) were simply fabricated by a wet impregnation using palladium nitrate. Physical properties of Pd/SiO₂ nanoparticles were studied by X-ray diffraction, energy-dispersive, X-ray analysis, N₂ adsorption and desorption isotherms and transmission electron microscopy. Results show a high dispersion of Pd nanoparticles with small size. Pd nanoparticles catalyzed very efficiently the hydrogenation of furfural to furfuryl alcohol with 76 % selectivity under mild conditions. Overall, the catalyst developed could find applications for the production of chemicals from biomass.     

Toxicity of acidization fluids used in California oil exploration

There has been considerable public interest regarding the toxicity of chemicals used in hydraulic fracturing, but little is known about its sister technique, acidizing. Little to no research has been done on what the chemicals of acidization are and what impact they could have on humans and the environment. This paper discusses the differences between three acidizing techniques (acid maintenance, matrix acidization, and acid fracturing) and quantifies the amounts of the chemicals used for each. Washington State's Quick Chemical Assessment Tool is used to identify F-graded toxins, which are known carcinogens, mutagens, reproductive toxins, developmental toxins, endocrine disruptors, or high acute toxicity chemicals. The analysis of the present data shows that there have been over 600 instances of acidizing in urbanized Southern and Central California from April 2013 to August 2015. Although most of the chemicals of acidizing are similar to hydraulic fracturing, those used most frequently are different. There are close to 200 specific chemicals used in acidization, with at least 28 of them being F-graded hazardous chemicals. Some are used frequently in the range of 100–1000 kg per treatment, such as hydrofluoric acid, xylene, diethylene glycol, and ethyl benzene. Close to 90 more chemicals are identified using non-specific names as trade secrets or reported with no quantity. Unlike hydraulic fracturing the chemical concentrations in acidizing are high, ranging from 6% to 18%, and the waste returns can be highly acidic, in the range of pH 0–3. With this paper it is hoped that acidization becomes part of the larger discussion on concerns with oil exploration and be evaluated by appropriate authorities.     

t-BuOK catalyzed bio-oil production from woody biomass under sub-critical water conditions

The substitution of fossil fuels and fossil-based products with biofuels and biomass-based products is indispensable for a sustainable society and a green environment. The liquefaction of biomass to produce biofuels under sub- and/or super-critical water conditions is one of the most promising methods that might allow this substitution. Here, for the first time, we report the results of the liquefaction of woody biomass under sub-critical water conditions at 250, 300, and 350 °C using potassium tert-butoxide (t-BuOK) as a catalyst. To compare and evaluate the catalytic performance of t-BuOK, the experiments were also performed under identical conditions using KOH as the catalyst. The product distributions obtained using either KOH or t-BuOK as the catalyst were very similar. The total oil yields increased and the solid residue yields decreased when either KOH or t-BuOK were used at reaction temperatures of 300 and 350 °C. The total bio-oil yields obtained at 300 °C with t-BuOK and KOH were 41.9 weight (%) and 43.0 weight (%), respectively, whereas the total bio-oil yield from the thermal run at 300 °C was approximately 24.0 weight (%). Although the O/C ratio of the raw material is 0.70, the O/C ratios of the light and heavy bio-oils obtained from the KOH catalytic run are 0.38 and 0.25, respectively. In addition, the O/C ratios for the light and heavy oils obtained from the t-BuOK catalyst are 0.41 and 0.26, respectively. We estimate that the heating values of the light and heavy bio-oils obtained by either catalytic run (t-BuOK or KOH) are approximately 24 MJ kg^?1 and 29 MJ kg^?1, respectively     

Immunotoxic manifestations in rats following inhalative exposure to furfural vapors

Furfural is an industrial compound used as a process intermediate and as a solvent; it poses a potential inhalation hazard in occupational settings. This study was carried out to find furfural-induced immunotoxicity in Wistar rat following inhalative exposure. The weights of thymus and lymph node were found decreased, while the weights of the liver and the adrenal gland were significantly increased following furfural exposure. Delayed-type hypersensitivity response was found decreased in furfural vapors-exposed animals when compared to that of control animals. The phagocytic index of peritoneal and alveolar exudates showed significant decrease and was most prominent (90%) in 30 days-exposed groups. The number of anti-rat anti-sheep red blood cell immunoglobulin M plaque forming cells of spleen got decreased in furfural-exposed groups in comparison to control. Taken together, this study indicates that inhalation of furfural induces immunotoxic manifestations that could lead to severe immunological disorders.     

A sustainable sulfate process to produce TiO2 pigments

Titanium dioxide (TiO₂) is a widely used white pigment. TiO₂ production in 2006 was about 1,400,000 metric tons in the USA. The two major processes to manufacture TiO₂ are the chloride process and the sulfate process. Currently, the TiO₂ industry finds the waste generated in the chloride process less than the waste generated in the sulfate process in its present design, despite generating large quantities of process-related carbon dioxide and carbon monoxide. As a consequence, the sulfate process appears less economical, notably due to the production of green vitriol, FeSO₄·7H₂O, as a major waste. Here, we describe a more sustainable sulfate process based on an earlier study on thermal decomposition of iron(II) sulfates. In the sustainable sulfate process, FeSO₄·7H₂O waste is used for greener production of sulfuric acid, H₂SO₄, used in turn for the digestion of ilmenite. Theoretical and actual yields of waste byproducts per metric ton of TiO₂ produced are used to show the environmental and economic advantages of the sustainable sulfate process.     

Efficiency of mercapto flavor compounds in removing acrylamide under high temperature and low humidity conditions

Acrylamide (AA) is a potential human carcinogen, genotoxicant, and neurotoxicant. Thus, the aim of this study was to examine the ability of mercapto flavor compounds to remove AA released from consumer packaging into food products. Four mercapto flavor compounds including 1,2-ethanedithiol, 1-butanethiol, 2-methyl-3-furanthiol, and 2-furanmethanethiol were employed to extract AA in model system using high temperature and low humidity. Our study showed that mercaptans were effective in eliminating AA in our model system. In order to remove 0.2 μmol AA, the optimal conditions in the reaction system were mercaptan flavor chemicals at 5 μmol, temperature 180 °C, and reaction time 25 min. In the presence of a higher pH, the greater was the amount of AA eliminated. Evidence indicates that employment of mercapto flavor chemicals under certain temperature and pH conditions is a reliable method to remove any unwanted AA from food products.     

Rapid photocatalytic degradation of the recalcitrant dye amaranth by highly active N-WO<Subscript>3</Subscript>

Dye wastewater is a major source of toxic aromatic amines released into the environment. Semiconductor photocatalysis is a clean, solar-driven process for the treatment of dye wastewater. To enhance applicability of semiconductor photocatalysis, the catalyst used should be visible light active. Here we report a facile synthesis of a highly visible-light-active nitrogen-doped tungsten oxide, N-WO₃, by thermal decomposition of peroxotungstic acid–urea complex. The structure and properties of N-WO₃ are characterized by X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy. The photodegradation of amaranth catalyzed by N-WO₃ is evaluated in a batch system under visible and ultraviolet A (UVA) light. Our results show successful doping of N in both interstitial and substitutional sites and the presence of N₂-like species. The N doping surprisingly expands the usable portion of the solar spectrum up to the near-infrared region and enhances the photocatalytic activity. At typical experimental conditions such as 25 mg/L of amaranth, 1 g/L of N-WO₃, and pH 7, 100 % degradation of amaranth is achieved within 2 h under both visible and UVA light. The photocatalytic activity of N-WO₃ is maintained in repeated cycles, indicating its exceptional photostability. To the best of our knowledge, this is the first time that a reusable, highly visible-light-active N-WO₃ can be obtained through thermal decomposition of peroxotungstic acid–urea complex.     

Application of eggshell waste for the immobilization of cadmium and lead in a contaminated soil

Liming materials have been used to immobilize heavy metals in contaminated soils. However, no studies have evaluated the use of eggshell waste as a source of calcium carbonate (CaCO₃) to immobilize both cadmium (Cd) and lead (Pb) in soils. This study was conducted to evaluate the effectiveness of eggshell waste on the immobilization of Cd and Pb and to determine the metal availability following various single extraction techniques. Incubation experiments were conducted by mixing 0–5% powdered eggshell waste and curing the soil (1,246 mg Pb kg^?1 soil and 17 mg Cd kg^?1 soil) for 30 days. Five extractants, 0.01 M calcium chloride (CaCl₂), 1 M CaCl₂, 0.1 M hydrochloric acid (HCl), 0.43 M acetic acid (CH₃COOH), and 0.05 M ethylendiaminetetraacetic acid (EDTA), were used to determine the extractability of Cd and Pb following treatments with CaCO₃ and eggshell waste. Generally, the extractability of Cd and Pb in the soils decreased in response to treatments with CaCO₃ and eggshell waste, regardless of extractant. Using CaCl₂ extraction, the lowest Cd concentration was achieved upon both CaCO₃ and eggshell waste treatments, while the lowest Pb concentration was observed using HCl extraction. The highest amount of immobilized Cd and Pb was extracted by CH₃COOH or EDTA in soils treated with CaCO₃ and eggshell waste, indicating that remobilization of Cd and Pb may occur under acidic conditions. Based on the findings obtained, eggshell waste can be used as an alternative to CaCO₃ for the immobilization of heavy metals in soils.     

Solvent-free biodiesel epoxidation

Biodiesel emerged again recently as an alternative for fossil fuels. Besides energy, biodiesel can be used as raw material to synthesize high value products such as epoxides. Indeed, epoxides are versatile intermediates in organic synthesis for numerous reactions due to the high reactivity of the oxirane ring. Actually common epoxidation by peracids in organic solvent can last several hours according to the double bonds number. The solvent confers selectivity to the reaction, preventing di-hydroxylation. Alternatively solvent-free reactions can be done in shorter times, but hydroxylation is less controlled. Here, we set up the synthesis of epoxides from methyl and ethyl esters of waste cooking oil, without solvent or metal catalyst. We tested molar ratio of hydrogen peroxide and formic acid, double bond number, reaction time, and temperature. Results show that the highest epoxide yields and selectivity, with high conversion of the double bonds, were obtained for temperature reactions between 50 and 65 °C, reaction times from 2 to 3 h, and molar ratio of 20/2/1. For those conditions, the double bonds conversion is equal or near 100 %, with epoxide yield and selectivity between 85 and 93 %. Organic solvent suppression, besides being environmentally friendly, also saves reaction time and subsequent purification steps.     

Tetrabromobisphenol A recovery from computer housing plastic by a new solvothermal process

Brominated flame retardants contained in electrical and electronic waste plastic are toxic to both humans and the environment. Most disposal technologies for brominated flame retardants are environmentally unfriendly. Here, a novel solvothermal process was designed to recover tetrabromobisphenol A, a typical brominated flame retardant, from waste computer housing plastic. The plastic waste was treated by the solvothermal process followed by vacuum rotary evaporation. Results show a tetrabromobisphenol A recovery efficiency of 78.9 %, and a purity of 95.6 %. The stability of tetrabromobisphenol A during the solvothermal process was confirmed by nuclear magnetic resonance. Kinetics showed that diffusion across the polymer layer controlled recovery. We conclude that the novel solvothermal process is a promising green way to recover tetrabromobisphenol A from electrical and electronic waste plastic.     

In vitro assessment of arsenic mobility in historical mine waste dust using simulated lung fluid

Exposure studies have linked arsenic (As) ingestion with disease in mining-affected populations; however, inhalation of mine waste dust as a pathway for pulmonary toxicity and systemic absorption has received limited attention. A biologically relevant extractant was used to assess the 24-h lung bioaccessibility of As in dust isolated from four distinct types of historical gold mine wastes common to regional Victoria, Australia. Mine waste particles less than 20 µm in size (PM₂₀) were incubated in a simulated lung fluid containing a major surface-active component found in mammalian lungs, dipalmitoylphosphatidylcholine. The supernatants were extracted, and their As contents measured after 1, 2, 4, 8 and 24 h. The resultant As solubility profiles show rapid dissolution followed by a more modest increasing trend, with between 75 and 82% of the total 24-h bioaccessible As released within the first 8 h. These profiles are consistent with the solubility profile of scorodite, a secondary As-bearing phase detected by X-ray diffraction in one of the investigated waste materials. Compared with similar studies, the cumulative As concentrations released at the 24-h time point were extremely low (range 297 ± 6–3983 ± 396 µg L^?1), representing between 0.020 ± 0.002 and 0.036 ± 0.003% of the total As in the PM₂₀.     

Valorization of agro-industrial fruit peel waste to fluorescent nanocarbon sensor: Ultrasensitive detection of potentially hazardous tropane alkaloid

• Transformation of agro-industrial waste to value-added material via green chemistry. • Orange peel is valorized into fluorescent nanodiamond-like carbon (fNDC) sensor. • fNDC detects potentially hazardous drug atropine sulfate (AS). • fNDC recognizes AS in biological fluids and pharmaceuticals. • fNDC assures applications in clinical and forensic toxicology. Millions of tonnes of agro-industrial waste are generated each year globally, with the vast majority of it going untreated, underutilized, and disposed of by burning or landfilling, causing severe environmental distress and economic downturn. A practical solution to this global issue is to use green chemistry to convert this waste into value-added products. Accordingly, in the present study, agro-industrial orange peel waste was valorized into fluorescent nanodiamond-like carbon sensor via a green route involving hydrothermal treatment of microwave carbonized orange peel waste. The developed sensor, used for the fluorescence detection of potentially hazardous drug atropine sulfate, exhibits unique dual linearity over concentration ranges of 300 nM to 1 M and from 1 M to 10 M, as well as ultra-low sensitivity of 34.42 nM and 356.46 nM, respectively. Additionally, the sensor demonstrates excellent reproducibility, high stability, and satisfactory recovery when used to identify and quantify atropine sulfate in biological samples and commercially available pharmaceuticals, indicating promising multidisciplinary applications.     

Size-dependent characterisation of historical gold mine wastes to examine human pathways of exposure to arsenic and other potentially toxic elements

Abandoned historical gold mining wastes often exist as geographically extensive, unremediated, and poorly contained deposits that contain elevated levels of As and other potentially toxic elements (PTEs). One of the key variables governing human exposure to PTEs in mine waste is particle size. By applying a size-resolved approach to mine waste characterisation, this study reports on the proportions of mine waste relevant to human exposure and mobility, as well as their corresponding PTE concentrations, in four distinct historical mine wastes from the gold province in Central Victoria, Australia. To the best of our knowledge, such a detailed investigation and comparison of historical mining wastes has not been conducted in this mining-affected region. Mass distribution analysis revealed notable proportions of waste material in the readily ingestible size fraction (≤250 µm; 36.1–75.6 %) and the dust size fraction (≤100 µm; 5.9–45.6 %), suggesting a high potential for human exposure and dust mobilisation. Common to all mine waste types were statistically significant inverse trends between particle size and levels of As and Zn. Enrichment of As in the finest investigated size fraction (≤53 µm) is of particular concern as these particles are highly susceptible to long-distance atmospheric transport. Human populations that reside in the prevailing wind direction from a mine waste deposit may be at risk of As exposure via inhalation and/or ingestion pathways. Enrichment of PTEs in the finer size fractions indicates that human health risk assessments based on bulk contaminant concentrations may underestimate potential exposure intensities.     

Recycling food and agriculture by-products to mitigate climate change: a review

Food loss and waste is a major issue affecting food security, environmental pollution, producer profitability, consumer prices, and climate change. About 1.3 billion tons of food products are yearly lost globally, with China producing approximately 20 million tons of soybean dregs annually. Here, we review food and agricultural byproducts with emphasis on the strategies to convert this waste into valuable materials. Byproducts can be used for animal and plant nutrition, biogas production, food, extraction of oils and bioactive substances, and production of vinegar, wine, edible coatings and organic fertilizers. For instance, bioactive compounds represent approximately 8–20% of apple pomace, 5–17% of orange peel, 10–25% of grape seeds, 3–15% of pomegranate peel, and 2–13% of date palm seeds. Similarly, the pharmaceutical industry uses approximately 6.5% of the total output of gelatin derived from fish bones and animal skin. Animals fed with pomegranate peel and olive pomace improved the concentration of deoxyribonucleic acid and protein, the litter size, the milk yield, and nest characteristics. Biogas production amounts to 57.1% using soybean residue, 53.7% using papaya peel, and 49.1% using sugarcane bagasse.

     

Stabilization of lead and copper contaminated firing range soil using calcined oyster shells and fly ash

A stabilization/solidification treatment scheme was devised to stabilize Pb and Cu contaminated soil from a firing range using renewable waste resources as additives, namely waste oyster shells (WOS) and fly ash (FA). The WOS, serving as the primary stabilizing agent, was pre-treated at a high temperature to activate quicklime from calcite. Class C FA was used as a secondary additive along with the calcined oyster shells (COS). The effectiveness of the treatment was evaluated by means of the toxicity characteristic leaching procedure (TCLP) and the 0.1 M HCl extraction tests following a curing period of 28 days. The combined treatment with 10 wt% COS and 5 wt% FA cause a significant reduction in Pb (>98 %) and Cu (>96 %) leachability which was indicated by the results from both extraction tests (TCLP and 0.1 M HCl). Scanning electron microscopy–energy dispersive X-ray spectroscopy (SEM–EDX) analyses are used to investigate the mechanism responsible for Pb and Cu stabilization. SEM–EDX results indicate that effective Pb and Cu immobilization using the combined COS–FA treatment is most probably associated with ettringite and pozzolanic reaction products. The treatment results suggest that the combined COS–FA treatment is a cost effective method for the stabilization of firing range soil.     

Isotopic evidences for microbiologically mediated and direct C input to soil compounds from three different leaf litters during their decomposition

We show the potentiality of coupling together different compound-specific isotopic analyses in a laboratory experiment, where ¹³C-depleted leaf litter was incubated on a ¹³C-enriched soil. The aim of our study was to identify the soil compounds where the C derived from three different litter species is retained. Three ¹³C-depleted leaf litter (Liquidambar styraciflua L., Cercis canadensis L. and Pinus taeda L., δ¹³C_vsPDB ≈ ?43‰), differing in their degradability, were incubated on a C4 soil (δ¹³C_vsPDB ≈ ?18‰) under laboratory-controlled conditions for 8 months. At harvest, compound-specific isotope analyses were performed on different classes of soil compounds [i.e. phospholipids fatty acids (PLFAs), n-alkanes and soil pyrolysis products]. Linoleic acid (PLFA 18:2ω6,9) was found to be very depleted in ¹³C (δ¹³C_vsPDB ≈ from ?38 to ?42‰) compared to all other PLFAs (δ¹³C_vsPDB ≈ from ?14 to ?35‰). Because of this, fungi were identified as the first among microbes to use the litter as source of C. Among n-alkanes, long-chain (C27–C31) n-alkanes were the only to have a depleted δ¹³C. This is an indication that not all of the C derived from litter in the soil was transformed by microbes. The depletion in ¹³C was also found in different classes of pyrolysis products, suggesting that the litter-derived C is incorporated in less or more chemically stable compounds, even only after 8 months decomposition.     

Sulfonated graphene nanomaterials for membrane antifouling,pollutant removal,and production of chemicals from biomass: a review

Water pollution and the unsustainable use of fossil fuel derivatives require advanced catalytic methods to clean waters and to produce fine chemicals from modern biomass. Classical homogeneous catalysts such as sulfuric, phosphoric, and hydrochloric acid are highly corrosive and non-recyclable, whereas heterogeneous catalysts appear promising for lignocellulosic waste depolymerization, pollutant degradation, and membrane antifouling. Here, we review the use of sulfonated graphene and sulfonated graphene oxide nanomaterials for improving membranes, pollutant adsorption and degradation, depolymerization of lignocellulosic waste, liquefaction of biomass, and production of fine chemicals. We also discuss the economy of oil production from biomass. Sulfonated graphene and sulfonated graphene oxide display an unusual large theoretical specific surface area of 2630 m²/g, allowing the reactants to easily enter the internal surface of graphene nanosheets and to reach active acid sites. Sulfonated graphene oxide is hydrophobic and has hydrophilic groups, such as hydroxyl, carboxyl, and epoxy, thus creating cavities on the graphene nanosheet’s surface. The adsorption capacity approached 2.3–2.4 mmol per gram for naphthalene and 1-naphthol. Concerning membranes, we observe an improvement of hydrophilicity, salt rejection, water flux, antifouling properties, and pollutant removal. The nanomaterials can be reused several times without losing catalytic activity due to the high stability originating from the stable carbon–sulfur bond between graphene and the sulfonic group.

     

Overview of principles and implementations to deal with spatial issues in monitoring environmental effects of genetically modified organisms

Background

Sorting and disposal of waste are the last steps in the “lifetime” of a product. If products are contaminated with chemicals assessed to be hazardous for man or environment, waste management has the role of a vacuum cleaner in substance chain management working in two different ways: The hazardous compounds have to be properly separated from potential secondary resources in sorting processes. If this is not possible, those products have to be disposed safely. Starting from the experiences collected with some chemicals banned, the tools used for phasing out these chemicals from the technosphere are studied with respect to their influence on the contamination of the environment.

Results

Even if a dangerous substance has been banned, it is further used in a number of products. In the cases presented here, the substances were banned for further use. In the case of CFCs, the substitutes used have partially also been substituted because of adverse effects. Besides the prohibition of use of hazardous substances, numerous other regulations were issued to reduce unsafe handling and minimize emissions into the environment. It turned out that waste management cannot correct mistakes which already happened “upstream” in the product chain. The control of point sources works quite successfully, whereas today the overwhelming emissions stem from diffuse sources, partially caused by unsafe waste management procedures.

Conclusions

Though there are no complete balances for both groups of compounds serving as examples, some conclusions can be drawn based on the experiences collected. Hazardous compounds may be separated successfully from used products or waste,

• If they are mostly used in industry and not in households,
• if they can be identified as part of certain products,
• if their concentration in these products is rather high,
• if technical problems come up when they contaminate secondary raw materials,
• if there is international support for proper waste management.

     

Adsorptive removal of rhodamine B from textile wastewater using water chestnut (Trapa natans L.) peel: adsorption dynamics and kinetic studies

Water chestnut peel, an agricultural bio-waste, was used as a biosorbent for removal of rhodamine B (RhB), basic textile dye, from an aqueous solution. The effects of various experimental parameters were studied. The equilibrium data correlated well with a Freundlich isotherm (R² = 0.98–0.99) followed by a Halsey isotherm model (R² = 0.98–0.99) which indicated heterogeneity of the adsorbent surface and multilayer adsorption of RhB dye onto the water chestnut peel waste (WCPW). High correlation coefficients (R² = 0.99) together with close agreement between experimental q_e (0.4–1.7 mg g^?1) and calculated q_e (0.4–2.5 mg g^?1) suggested that the adsorption process followed pseudo-second-order kinetics, with k₂ values in the range of 52–3.4 × 10^?1 g mg^?1 min^?1 at different concentrations. The overall mechanism of adsorption was controlled by both liquid-film and intra-particle diffusions. The negative values of change in Gibb's free energy (?ΔG⁰ = 19.2–29.2 kJ mol^?1) and positive values of change in enthalpy (ΔH⁰ = 30.9–117.6 kJ mol^?1) revealed the process to be spontaneous and endothermic. WCPW was found to be an effective adsorbent for removal of RhB, a cationic dye, from an aqueous solution.     

Waste control by waste: efficient removal of bisphenol A with steel slag,a novel activator of peroxydisulfate

Activated persulfates are efficient reagents for oxidation of organic contaminants and water treatment. Various compounds are currently used to activate persulfates, but there is a need for cheap and efficient activators. Here, we report the first use of steel slag, an industrial solid waste, as a solid activator for peroxydisulfate activation. We tested this system for bisphenol A degradation. Results indicate that about 70% of bisphenol A can be removed within 1 h. Conditions were 50 μg/L of bisphenol A, 2 g/L of peroxydisulfate, 3 g/L of steel slag and temperature of 298 K. The components and surface morphology of unused and recycled steel slag were analyzed by X-ray diffraction and scanning electron microscopy, whereas the main reactive oxygen species were elucidated by using radical scavengers. Findings show that both base oxides and iron oxides are responsible for peroxydisulfate activation. A redox mechanism involving liquid and solid phases is proposed. Overall, this study reveals the successful recycling of steel slag to activate persulfates for water treatment, following the principle of ‘waste control by waste.’