Dynamics of diesel fuel degradation in contaminated soil using organic wastes

Bioremediation is an effective measure in dealing with such contamination, particularly those from petroleum hydrocarbon sources. The effect of soil amendments on diesel fuel degradation in soil was studied. Diesel fuel was introduced into the soil at the concentration of 5 % (w/w) and mixed with three different organic wastes tea leaf, soy cake, and potato skin, for a period of 3 months. Within 84 days, 35 % oil loss was recorded in the unamended polluted soil while 88, 81 and 75 % oil loss were recorded in the soil amended with soy cake, potato skin and tea leaf, respectively. Diesel fuel utilizing bacteria counts were significantly high in all organic wastes amended treatments, ranging from 111 × 106 to 152 × 106 colony forming unit/gram of soil, as compared to the unamended control soil which gave 31 × 106 CFU/g. The diesel fuel utilizing bacteria isolated from the oil-contaminated soil belongs to Bacillus licheniformis, Ochrobactrum tritici and Staphylococcus sp. Oil-polluted soil amended with soy cake recorded the highest oil biodegradation with a net loss of 53 %, as compared to the other treatments. Dehydrogenase enzyme activity, which was assessed by 2,3,5-triphenyltetrazolium chloride technique, correlated significantly with the total petroleum hydrocarbons degradation and accumulation of CO₂. First-order kinetic model revealed that soy cake was the best of the three organic wastes used, with biodegradation rate constant of 0.148 day^?1 and half life of 4.68 days. The results showed there is potential for soy cake, potato skin and tea leaf to enhance biodegradation of diesel in oil-contaminated soil.     

Sugar and alcohol industrial waste as low-cost adsorbents: application in situ for remediation of potentially toxic metals

Filter cake, a residue from the ethanol industry, has a high content of organic matter and presents promising characteristics to act in the remediation of potentially toxic metals. The objective of this paper was to evaluate the characteristics of humic materials extracted from filter cake and investigate their interaction with toxic metals and apply to filter cake in natura and in situ. The complexation capacity of humic matter extracted from filter cakes indicated their high chelating potential and the organic matter importance in potentially toxic metals’ complexation capacity of this type of material. The humic substances extracted from filter cakes showed different affinities for potentially toxic metals (humic material Alagoas: Cr < Ni < Cd < Cu < Pb and humic material from São Paulo: Cd < Ni < Cr < Cu < Pb). Although the affinity order of the metals by humic material has been different from the data obtained from the controlled conditions (laboratory), “in situ” studies showed a high retention of potentially toxic metals by adsorptive materials.     

A cleaner and eco-benign process for wool dyeing with madder, <Emphasis Type="Italic">Rubia tinctorum</Emphasis> L., root natural dye

In this study, an alternative cleaner process over traditional metallic mordanting process for wool dyeing with madder, Rubia tinctorum L., root natural dye was presented. Wool surface was modified with novel eco-friendly and biocompatible cationizing agent having numerous free amine groups, namely chitosan–polypropylene imine dendrimer hybrid (CS-PPI). Modified wool demonstrated remarkable increase in dye uptake as compared to raw wool. Optimal dyeing results were obtained when CS-PPI 7 %, madder dye 20 % and dyeing pH 7 were employed. Dyeing results such as percent dye exhaustion and color depth emphasized auxiliary agents, i.e., metallic mordant and acid could be eliminated from wool dyeing process with madder dye. Saturation point shifted to lower dye concentrations in the treated wool suggested the same color depth could be obtained using lower amount of crude dye material. Wool modification with CS-PPI demonstrated no adverse impact on other properties such as colorfastness and color shade characteristics. In addition, treated wool exhibited excellent antimicrobial activity (nearly 100 % microbial reduction) against two common pathogenic microorganisms, Escherichia coli and Staphylococcus aureus which were almost durable after dyeing and subsequent repeated washes. In general, the results of this investigation showed that CS-PPI can be employed as an alternative eco-friendly “bio-mordant” as well as effective antimicrobial finishing material in wool dyeing with madder dye.     

Biogenic silver nanoparticles on carbonaceous material from sewage sludge for degradation of methylene blue in aqueous solution

Silver nanoparticles (Ag NPs) were synthesized in situ, using a one-step green methodology with Camellia sinensis (green tea) aqueous extract as reducing agent, and supported on a carbonaceous material (Ag-CM), originated from the pyrolysis of sewage sludge. UV–Vis spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy and Brunauer–Emmet–Teller were used to characterize the nanocomposite. Ag-CM composite exhibited very good catalytic activity in the degradation process of methylene blue (MB) dye in aqueous solution without using sunlight or UV radiation. Batch kinetic and isothermal experiments, using 30 mg/L MB solution, showed that Ag-CM composite removed near to 91 % of MB in 9 h, whereas the carbonaceous material alone removed only 60 % in 30 h. Experimental data were adjusted to different kinetic and isotherms models, where both materials fit the second-order and Langmuir–Freundlich models, respectively; therefore, a chemisorption mechanism probably occurs in these heterogeneous materials.     

Experimental evidence for eukaryotic fossil preservation: Onion skin cells in silica solution

Research on the origin of eukaryotes often focuses on the exceptional preservation found in silicified Precambrian fossils. Nuclei like subcellular structures in well-preserved fossil becomes confusion and arguments, which focus on whether the partial degradation of prokaryotes produces artifacts that resemble a ‘nucleus’, or fossilized nuclei of eukaryotes. In order to understand the mechanisms of silicification and identify the fossilized subcellular and microstructures in rocks, a series of laboratory controlled experiments were performed for simulating the silicification process. The effects of different silica solutions in eukaryote fossilization were studied in our experiments by exposing onion skin cells (epidermis) to silica solutions. Onion skin provides a good experimental model because of its well characterized cellular structures which are easily observed. The designed experiments revealed that the possibility of onion cell preserved as a “fossil” with nuclear structures, the first week fossilization, or mineralization as rapid as 1 week is important. And the experiment also revealed interactions between silica and the onion skin cell wall surface functional groups were weak. The preservation of nuclei in the onion skin model was due to precipitation in highly supersaturated silica solutions rather than simply the high silica concentration. When the silica gel precipitates slowly at low supersaturation states, the nuclei were not well preserved, but the rapid precipitation at high supersaturated silica conditions preserved nuclear structures. A better understanding of the processes involved in onion skin fossilization will further contribute to issues concerning the silicification of other eukaryotic materials.     

Coagulant proteins identified in Mustard: a potential water treatment agent

The use of natural coagulant protein in drinking water treatment has been discussed for a long time, though the method is still not in practice, probably due to limited knowledge and availability of material. In the present work, different Mustard varieties were tested for the presence of coagulant protein compared with Moringa seed extract and their potential application in water treatment. The coagulation activity of the protein extract was measured using synthetic clay solution as well as water from pond. The protein content was determined by Bradford method, molecular mass determined by Sodium dodecyl sulfate–polyacrylamide gel electrophoresis, and peptide sequence was analyzed by Mass spectrometry. Extract of Mustard (large) and Moringa seed showed coagulation activity of ?70 and ?85 % after 90 min, respectively. Interestingly, seed extracts from other Mustard varieties had coagulation activity after heat activation at 95 °C for 5 h. However, the coagulation activity of Mustard seed extract against turbid pond water was higher (?60 %) compared to Moringa seed extract (?50 %). The peptide sequence analysis of 6.5 and 9 kDa proteins was found to be homologous to Moringa coagulant protein and napin3, respectively. To our knowledge, this could be the first report on Mustard seed having coagulant protein. The coagulation activity of Mustard (large) against highly turbid pond water suggested that it could be a potential natural coagulant for water treatment.     

Biosorption of ammoniacal nitrogen from aqueous solutions with low-cost biomaterials: kinetics and optimization of contact time

The biosorption of ammoniacal nitrogen (N-NH₄ ⁺) from aqueous solutions by dead biomass of brown seaweed Cystoseira indica and Jatropha oil cake (JOC), which is generated in the process of biodiesel recovery from its seeds, was studied under diverse experimental conditions. The N-NH₄ ⁺ biosorption was strictly pH dependent, and maximum uptake capacity of C. indica (15.21 mg/g) and JOC (13.59 mg/g) was observed at initial pH 7 and 3, respectively. For each biosorbent–N-NH₄ ⁺ system, kinetic models were applied to the experimental data to examine the mechanisms of sorption and potential rate-controlling steps. The generalized rate model and pseudo-second-order kinetic models described the biosorption kinetics accurately, and the sorption process was found to be controlled by pore and surface diffusion for these biosorbents. Results of four-stage batch biosorber design analysis revealed that the required time for the 99 % efficiency removal of 40 mg/L N-NH₄ ⁺ from 500 L of aqueous solution were 76 and 96 min for C. indica and JOC, respectively. The Fourier transform infrared spectroscopy analysis before and after biosorption of ammonium onto C. indica and JOC revealed involvement of carboxylic and hydroxyl functional groups.     

Seasonal to sub-seasonal palaeoenvironmental changes in Lake Sihetun (Lower Cretaceous Yixian Formation, NE China)

Sedimentary properties of the fossil-bearing deposits of Lake Sihetun (Yixian Formation, Lower Cretaceous) were investigated on a high-resolution, sub-millimetric scale. Data were obtained from three excavations and 50 thin-sections. Lake evolution is subdivided into four phases, of which Phases 2 and 3 provided suitable conditions for excellent fossil preservation. Six microfacies are recognized within these two phases: (1) allochthonous, siliciclastic laminae (26.1 μm thick on average), (2) chrysophycean cyst accumulations, (3) tuffaceous silt, (4) lacustrine chemical precipitates, (5) tuff and (6) normal-graded, sandy to silty siliciclastics. Phase 2 is characterized by Microfacies 1–5 and Phase 3 by Microfacies 6. Biofilms are common, and mass occurrences of framboids (pyrite pseudomorphs) are occurring in sediments of Phase 2. Varves can be verified for Microfacies 2 and 4 (179 μm thick). Thicknesses of Microfacies 2 highly fluctuate depending on the occurrence of seasonal heavier rains, which led to deposition of tuffaceous silt layers (Microfacies 3). Meromictic conditions dominated Phase 2, but recurrent mixing is demonstrated by short-lived colonization events by a benthic invertebrate fauna. The transition of Phase 2 to holomictic Phase 3 is marked by a dramatic increase in sediment yield associated with a change from dry to humid climates. Fossil preservation differs according to the diverse physical and chemical conditions during lake evolution. Phase 2 yields framboid replacement of organic tissue and excellent preservation of growth increments of clam-shrimp carapaces, which are poorly preserved in Phase 3. Conversely, though exhibiting a different mode of preservation, insect fossils are superbly preserved as dark stains sealed by silica coatings during Phase 3.     

Evaluation of permethrin-impregnated military uniforms for contact toxicity against mosquitoes and persistence in repeated washings

The loss of permethrin from impregnated uniforms due to repeated washings was studied by chromatographic estimation of the residues. The mean (± SE_mean) percentage losses of permethrin after one to five washings were 16.7 ± 2.3, 22.5 ± 3, 29.6 ± 2.9, 40.2 ± 2 and 52.2 ± 2.4, respectively. The reduction in contact toxicity against mosquitoes after each washing was studied by World Health Organization tube and cone bioassays against Aedes albopictus mosquitoes. The median knockdown time for 5-min exposure to the treated uniforms increased from 5.9 to 71.8 min after five washings. Mosquito mortality 24 h post-exposure in cone bioassays was <80 % after the fifth washing, indicating the loss of efficacy. The uniforms need to be retreated after five washings so as to ensure adequate protection against disease vectors. The washing water should be properly disposed off to prevent environmental contamination and toxicity to aquatic organisms. Methods for treatment of military uniforms, which ensure high resistance to washing, need to be adopted so as to avoid frequent re-impregnations with permethrin.     

Adsorption kinetic models for the removal of Cu(II) from aqueous solution by clay liners in landfills

Liners are commonly used in engineered waste disposal landfill to minimize the potential contamination of the aquatic environment. The adsorption behavior of Cu(II) from aqueous solution onto clay admixed with various mix ratios of quarry fines was investigated. The amount of Cu(II) adsorption increases with increase in contact time. The copper removal efficiencies of the composite mixture gradually decrease from 94.53 % (raw clay) to 85.59 % (20 % of quarry fines with clay), and appreciable decrease in percent removal 75.61 % was found with 25 % of quarry fines with clay. The kinetic adsorption data were analyzed by pseudo-first-order, pseudo-second-order, Bhattacharya–Venkobachar and Natarajan–Khalaf kinetic models to classify adsorption process mechanisms. Kinetic experimental data were good agreement with pseudo-second-order kinetic model with the degree of fitness of the data (R ²) 0.9999 for the adsorption of Cu(II). The results revealed that quarry fines can be used with optimum of 20 % replacement of natural clay for removal of Cu(II) as a liner material in landfills.     

Plasmon resonance-enhanced internal reflection ellipsometry for the trace detection of mercuric ion

Mercuric ion in aqueous media is extremely toxic to the environment and organisms. Surface plasmon resonance-based optical sensors have been reported that can detect low concentrations as low as fg analytes per cm² of the sensor surface. Moreover, the ellipsometry, which detects the changes in polarization states of reflected light from the sensor surface, can be combined with SPR technique to figure out the changes in dielectric media beneath the sensor surface. In this paper, this technique called as surface plasmon resonance-enhanced total internal reflection was used to make trace monitoring of mercuric ion in aqueous media. A protein and an aptamer-based biosensor were developed for this purpose. Bovine serum albumin and mercury-specific aptamer were immobilized on sensor chip via self-assembly routes. The limit of detection was 40.7 nM Hg²⁺ for protein sensor and 26 pM Hg²⁺ for anti-Hg aptamer-based sensor. The selectivity of the protein sensor was lower than anti-Hg aptamer sensor when Pb²⁺ ion was used as the competent ion.     

Effect of the activation temperature over activated carbon production from castor cake and its evaluation as dye adsorbent

In this work, castor cake produced as a by-product in castor oil extraction was used for activated carbon production. Castor cake was chemically treated with a K₂CO₃ solution, and the effect of the pyrolysis temperature in the 500–900 °C range was studied. Materials were characterized by X-ray powder diffraction, thermogravimetric analysis, scanning electron microscopy and nitrogen adsorption–desorption at ?196 °C. Methylene blue adsorption was selected as a test probe to stress the removal capacity of the prepared materials. By the X-ray powder diffraction analysis, carbon obtaining in its graphite allotropic form together with other inorganic compounds was verified. Scanning electron microscopy images evidenced the generation of porosity in the thermally treated samples compared with the pristine compound. In addition, the specific surface area values augmented progressively with the thermal treatment increment achieving a value of 1015 m² g^?1 in the 900 °C calcined sample. Calcination at 800 °C and m/V = 0.003 ratio were the best parameter combination to achieve a 99.6% methylene blue uptake.     

Off-line solid-phase extraction procedure for the determination of polycyclic aromatic hydrocarbons from aqueous matrices

An off-line solid-phase extraction procedure followed by high-performance liquid chromatography with ultraviolet detection for the determination of 16 priority polycyclic aromatic hydrocarbon pollutants in aqueous matrices was described. Diverse aspects determining extraction efficiency such as packing type (disk or cartridge), elution solvents and addition of organic modifiers to the sample were evaluated. Elution with acetonitrile yields the highest recoveries. Rinsing the sample bottle with acetonitrile and combining the rinse with the sample extract avoids the adsorption of polycyclic aromatic hydrocarbons on the walls of the water containers. The use of isopropanol or methanol 10 % (V/V) was the most appropriate amount for the enrichment of 2- to 6-ring aromatic compounds only on C18 cartridge. The recoveries for all studied polycyclic aromatic hydrocarbons are ranged from 71.4 to 95.2 % for a treated water samples of 500 mL. The proposed method gives very low detection limits (subnanograms per liter) and it has been applied to drinking water, surface water and industrial effluent (oil refinery) samples with good results.     

Formation process of a large paleolandslide-dammed lake at Xuelongnang in the upper Jinsha River,SE Tibetan Plateau: constraints from OSL and <Superscript>14</Superscript>C dating

A large number of the landslide dams located on the major rivers at the southeastern margin of the Tibetan Plateau have been previously identified through remote sensing analysis and field investigations. The Xuelongnang paleolake was one of the lakes formed by these landslide dams in the upper Jinsha River, where the association of a relict landslide dam, lacustrine sediment, and outburst sediment is well preserved. This preservation provides an opportunity to better understand the formation, evolution, and longevity of a large landslide-dammed lake in the upper Jinsha River. It was inferred that the Xuelongnang dammed lake may have been formed by an earthquake-induced paleoavalanche. The surface area of the lake at its peak was estimated at 7.0?×?10⁶ m², and the corresponding volume was approximately 3.1?×?10⁸ m³. Two outburst flood events were determined to have occurred during the life span of the lake. Based on the 18 ages obtained from optically stimulated luminescence (OSL) and carbon-14 (¹⁴C) dating combined with stratigraphic sequences observed in the field, the paleolandslide-dammed lake was formed at approximately 2.1 ka and subsequently breached locally. The dammed lake was sustained for a period of some 900 years based on the chronological constraining. This study confirms that a major landslide-dammed lake can be sustained for at least hundreds of years and breached by several dam breaks in multiple periods, which contributed to the preservation of the knickpoints at millennial scale along the major rivers in the study area.     

Burial and Preservation of Carbonate Rocks Over Phanerozoic Time

Comparison of results for the original burial rate of carbonate sediments over Phanerozoic time, as calculated using the GEOCARBSULFvolc model, with their rate of preservation to the present (survival rate) shows a considerable loss of mass, partly by subduction of oceanic crust, during the past 250 million years. Before that time, despite the evidence that preserved Paleozoic carbonates appear to have been deposited only in shallow water, we contend that there was also inorganic deposition of carbonates in the Paleozoic deep sea with subsequent loss by subduction. Inorganic carbonate deposition may have been abetted by the vastly different seawater and atmospheric composition for most of the Paleozoic than those of post-Cretaceous and end Paleozoic–early Mesozoic times. The hypothesis helps to explain the loss of mass greater than that predicted for shallow-water carbonates prior to 250 Ma.     

Recycled concrete aggregate coated with quaternary ammonium compounds for water disinfection

Growing demand for point-of-use water treatment including greywater recycling as well as appropriate disinfection without formation of harmful disinfection byproducts (DBPs) calls for new methods of efficient microbial control. In recent years, antimicrobial nanomaterials (NMs) have been widely studied as a potential alternative to traditional chlorine disinfection, yet concerns over their releases to environments and subsequent impacts have limited their use on a large scale. In this work, recycled concrete aggregate (RCA) was proposed as a sustainable and environmentally friendly disinfecting substrate for water disinfection by coating with a composite of silica-quaternary ammonium compound (Fixed-Quat). Two different types (gel and particle) of Fixed-Quat were applied to RCA, and their adherence and antimicrobial activities were compared each other. When using E. Coli as a model bacterial pathogen, the Fixed-Quat gel and particle coated RCA materials showed similar and effective microbial inactivation performance with a rate of 2.0 × 10^?3 (gel) and 1.82 × 10^?3 (particle) log reduction cm^?2 min^?1. By potentially eliminating regulated DBPs formation and minimizing release of NMs into the environment, the antimicrobial coated RCA would be a promising and sustainable alternative to conventional disinfection methods in engineered aquatic systems.     

Heavy metal exposure from co-processing of hazardous wastes for cement production and associated human risk assessment

This study was carried out to determine the concentration of heavy metals (Cd, Ni, Pb, Cr, Ni and Zn) in ordinary Portland cement (OPC) produced from the co-processing with hazardous waste in comparison with OPC produced using natural raw materials. The results showed that the concentration of heavy metals in cement produced from natural raw material was in the order of Zn > Pb > Cr > Ni > Cu > Cd. Zn and Cd were the highest and the lowest concentrations, respectively, in cements produced from the co-processing activity. The difference between heavy metals concentrations in OPC produced with and without co-processing was found to be statistically significant. The concentration of heavy metals in the cement produced is generally factory dependent. The human risk assessment associated with the heavy metals for non-carcinogenic and carcinogenic risks has been evaluated. The calculated hazard index (HI) and total lifetime cancer risks (LCR) were lower than the acceptable threshold reference values, HI < 1 and LCR < 1 × 10^?4, respectively. Thus, it is anticipated that there is no potential of non-carcinogenic and carcinogenic risks for both adult and children. However, the findings indicated that there is a need for regulatory monitoring. The exposure pathway for both non-carcinogenic and carcinogenic risks are both in the order of ingestion > dermal > inhalation.     

Comparative study of the absorptive potential of raw and activated carbon <Emphasis Type="Italic">Acacia nilotica</Emphasis> for Reactive Black 5 dye

Acacia nilotica was used for the adsorption of Reactive Black 5 (RB5) dye from an aqueous solution. Both the raw and activated (with H₃PO₄) carbon forms of Acacia nilotica (RAN and ANAC, respectively) were used for comparison. Various parameters (including dye concentration, contact time, temperature, and pH) were optimized to obtain the maximum adsorption capacity. RAN and ANAC were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The maximum experimental adsorption capacities for RAN and ANAC were 34.79 and 41.01 mg g^?1, respectively, which agreed with the maximum adsorption capacities predicted by the Langmuir, Freundlich, and Dubinin–Radushkevich equilibrium isotherm models. The adsorption data of ANAC showed a good fit to the isotherm models based on the coefficient of determination (R ²): Langmuir type II (R ² = 0.99) > Freundlich (R ² = 0.9853) > Dubinin–Radushkevich (R ² = 0.9659). This result suggested monolayer adsorption of RB5 dye. The adsorption of RB5 dye followed pseudo-second-order kinetics. The RAN adsorbent reflected an exothermic reaction (enthalpy change, ΔH = ?0.006 kJ mol^?1) and increased randomness (standard entropy change, ΔS = 0.038 kJ mol^?1) at the solid–solution interface. In contrast, ANAC reflected both exothermic [?0.011 kJ mol^?1 (303–313 K)] and endothermic [0.003 kJ mol^?1 (313–323 K)] reactions. However, the ΔS value of ANAC was lower when the RB5 adsorption increased from 313 to 323 K. The negative values for the Gibbs free energy change at all temperatures indicated that the adsorption of RB5 dye onto RAN and ANAC was spontaneous in the forward direction.     

煤层气井井斜角对隔水层界面胶结强度影响试验

为了控制煤层气井开采过程中的水窜问题,采用自主设计的试验装置对沁水盆地晋城地区煤层气样品进行模拟试验,获得了井斜角分别为0°、30°、60°、90°条件下隔水层界面胶结强度试验数据,分析了井斜角对隔水层界面胶结强度的影响机理。结果表明:隔水层界面胶结强度随井斜角的增大而降低,原因是随着井斜角增大,井壁的泥饼环上部依次变薄,下部依次变厚,井斜角到90°时达到最厚,且随着泥饼的变厚,泥饼成分中黏土矿物的成分逐渐减少,钻屑和重晶石的含量逐渐增多。分析还认为,影响隔水层界面胶结强度主要因素有黏聚力、泥饼的含水率、颗粒密实程度、颗粒结构和矿物成分。因此,煤层气井型对隔水层界面胶结强度的影响较大,即若采用水平井开采煤层气,可能水窜问题更突出。      

Removal of phosphates from aqueous solution by sepiolite-nano zero valent iron composite optimization with response surface methodology

In this study, sepiolite-nano zero valent iron composite was synthesized and applied for its potential adsorption to remove phosphates from aqueous solution. This composite was characterized by different techniques. For optimization of independent parameters (pH = 3–9; initial phosphate concentration = 5–100 mg/L; adsorbent dosage = 0.2–1 g/L; and contact time = 5–100 min), response surface methodology based on central composite design was used. Adsorption isotherms and kinetic models were done under optimum conditions. The results indicated that maximum adsorption efficiency of 99.43 and 92% for synthetic solution and real surface water sample, respectively, were achieved at optimum conditions of pH 4.5, initial phosphate concentration of 25 mg/L, adsorbent dosage of 0.8 g/L, and 46.26 min contact time. The interaction between adsorbent and adsorbate is better described with the Freundlich isotherm (R ² = 0.9537), and the kinetic of adsorption process followed pseudo-second-order model. Electrostatic interaction was the major mechanisms of the removal of phosphates from aqueous solution. The findings of this study showed that there is an effective adsorbent for removal of phosphates from aqueous solutions.