Rapidly reducing cadmium from contaminated farmland soil by novel magnetic recyclable Fe3O4/mercapto-functionalized attapulgite beads.

Reducing cadmium (Cd) content from contaminated farmland soils remains a major challenge due to the difficulty in separating commonly used adsorbents from soils. This study synthesized novel millimeter-sized magnetic Fe3O4/mercapto-functionalized attapulgite beads (MFBs) through a facile one-step gelation process incorporating alginate. The MFBs inherit the environmental stability of alginate and enhance its mechanical strength by hybridizing Fe3O4 and clay mineral components. MFBs can be easily separated from flooded soils by magnets. When applied to 12 Cd-polluted paddy soils and 14 Cd-polluted upland soils, MFBs achieved Cd(II) removal rates ranging from 16.9% to 62.2% and 9.8%-54.6%, respectively, within a 12-h period. The MFBs predominantly targeted the exchangeable and acid soluble, and reducible fractions of Cd, with significantly enhanced removal efficiencies in paddy soils compared to upland soils. Notably, MFBs exhibited superior adsorption performance in soils with lower pH and organic matter (OM) content, where the bioavailability and mobility of Cd are heightened. The reduction of Cd content by MFBs is a sustainable and safe method, as it permanently removes the bioavailable Cd from soil, rather than temporarily reducing its bioavailability. The functional groups such as -SH, -OH, present in attapulgite and alginate of MFBs, played a crucial role in Cd(II) adsorption. Additionally, attapulgite and zeolite provided a porous matrix structure that further enhanced Cd(II) adsorption. The results of X-ray photoelectron spectroscopy suggested that both chemical precipitation and surface complexation contributed to Cd(II) removal. The MFBs maintained 87.6% Cd removal efficiency after 5 regeneration cycles. The surface of the MFBs exposed new adsorption sites and increased the specific surface area during multiple cycles with Cd-contaminated soil. This suggests that MFBs treatment with magnetic retrieval is a potentially effective pathway for the rapid removal of Cd from contaminated farmland soils.

Application of extracellular polymers on soil communities exposed to oil and nickel contamination.

The petrochemical industry is responsible for many accidental releases of pollutants in soil such as hydrocarbons and toxic metals. This co-contamination is responsible for a delay in the degradation of the organic pollution. Many successful technologies to remove these metals apply extracellular polymeric substances (EPS). In this study, we tested the application of an EPS from a Paenibacillus sp. to aid the bioremediation of soils contaminated with crude oil and nickel. We conducted a microcosm experiment to soils containing combinations of oil, nickel, and EPS. The final concentration of oil was evaluated with an infrared spectrometer. Also, we sequenced the metagenomes of the samples in an ion torrent sequencer. The application of EPS did not aid the removal of hydrocarbons with or without the presence of nickel. However, it led to a smaller decrease in the diversity indexes. EPS decreased the abundance of Actinobacteria and increased that of Proteobacteria. The EPS also decreased the connectivity among Actinobacteria in the network analysis. The results indicated that the addition of EPS had a higher effect on the community structure than nickel. Altogether, our results indicate that this approach did not aid the bioremediation of hydrocarbons likely due to its effect in the community structure that affected hydrocarbonoclastic microorganisms.

Degradation of ammonia from gas stream by advanced oxidation processes.

The reduction of ammonia emissions from air was experimentally investigated by advanced oxidation processes (AOPs) utilizing the combination of ultraviolet irradiation with ozone. The influence of operating conditions such as initial ammonia concentration and flow rate of gas on the reduction of ammonia concentration was investigated in homemade photochemical unit. The conversion of ammonia decreased with increasing initial concentration of ammonia and with increasing flow rate of air (decreasing retention time). The highest conversion of ammonia (97%) was achieved under lower initial concentration of ammonia (30 ppm) and lower flow rate of air (28 m3/h). The energy per order was evaluated for the advanced oxidation process too. The energy consumption was about 0.037 kWh/m3/order for the 97% ammonia conversion at 30 ppm of initial ammonia concentration and 28 m3/h flow rate of air. Based on the results, the advanced oxidation process combining the UV irradiation and ozone was effective for mitigation of ammonia concentration and presents a promising technology for the reduction of odor emissions from livestock buildings. Moreover, the AOPs are suitable for application for high flow rate of air, especially for ammonia abatement from livestock buildings, where very high efficiency is expected.

Modeling and optimization of process variables for HCl gas removal by response surface methodology.

In the present article, optimization of process variables has been done to maximize the removal efficiency of toxic HCl gas in a submerged self-priming venturi scrubber. Response surface methodology with central composite design has been chosen to predict the effect of process variables on the removal efficiency. A quadratic equation was found from this study to predict the removal efficiency and from the ANOVA test, the significance of process variables was evaluated. Regression analysis confirmed the suitability of the developed model by the higher R2 square value (0.9717). Optimum conditions were obtained as 55.18 m s-1 of throat gas velocity, 405.10 ppm of inlet HCl concentration and 0.0038 N of NaOH concentration in scrubbing liquid to achieve 90.80% of the HCl removal efficiency.

Gaseous formaldehyde removal: A laminated plate fabricated with activated carbon, polyimide, and copper foil with adjustable surface temperature and capable of in situ thermal regeneration.

Formaldehyde is one of the most common indoor air pollutants in Chinese residences. This study introduces a novel laminated plate with adjustable surface temperature to remove gaseous formaldehyde. The plate is fabricated with activated carbon, polyimide, and copper foil via thermal compression. The plate can be regenerated in situ by applying a direct current to the copper foil. Adsorption-regeneration cycle tests were conducted to evaluate the plate's formaldehyde removal performance. The overall removal efficiency of the fabricated laminated plate with glue mass fraction of 25% and thickness of 1.5 mm was about 30% at the face velocity of 0.8-1.2 m/s. The pressure drop was about 5 Pa. Its removal ability can be regenerated in situ in 8 minutes by increasing the surface temperature to 80°C. The fabricated laminated plate showed good durability after 52 cycles of adsorption-regeneration tests. The results indicate that the proposed laminated plate can enhance the purifying efficiency and enlarge the life span of ordinary, cheap sorbents. It makes cheap materials with low performance suitable for air purification.

An explanation of soil amendments to reduce cadmium phytoavailability and transfer to food chain.

Cadmium contamination in soil, water and food has become a global problem since last century's industrial and agricultural revolution. It is a highly toxic metal with serious consequences on human and animal health. Different natural and anthropogenic sources are responsible for Cd release in the soil which ultimately leads to the food chain. Cd persists in soil for long durations due to its minimal microbial or chemical loss. There are various physical, chemical or biological techniques which are helpful to minimize Cd risk in food chain. Among them, in-situ immobilization with organic, inorganic or clay amendments is a cost-effective and an environment friendly strategy to remediate Cd polluted sites. Lime, biochar, organic wastes, phosphorus fertilizers, sepiolite, zeolite, hydroxyapatite and bentonite are commonly used amendments for amelioration of Cd contaminated soils. These amendments reduce Cd uptake and enhance immobilization by adsorption, complexation, and precipitation processes. This review is aimed to provide a comprehensive note on Cd toxicity in humans and environment, its immobilization by different agents through variety of processes, and comparison of technologies for Cd removal from contaminated sites.

Plant polyphenol-inspired nano-engineering topological and chemical structures of commercial sponge surface for oils/organic solvents clean-up and recovery.

In our study, plant polyphenol-inspired chemistry is explored to nano-engineer the topological and chemical structures of commercial melamine sponge surface for preparing superhydrophobic sponges. Briefly, tannic acid (TA, a typical plant polyphenol) is applied to induce the co-assembly of silica nanoparticles (SiO2) and silver ions (Ag+) to form SiO2@TA@Ag nanostructures on a melamine sponge surface. After further chemical fluorination, the superhydrophobic sponge with a "lotus leaf-mimic" surface is formed. Surface topological/chemical structures, superhydrophobic property and anti-combustion characteristics of the sponge are examined by a series of characterization techniques, including scanning electron microscopy, X-ray photoelectron spectroscopy, water contact angle measurements, combustion/heating test, etc. The superhydrophobic sponge presents an adsorption capacity of 69-153 times of its own weight toward various oils/organic solvents, and exhibits excellent recycling ability evidenced by over 100-cycled uses. Continuous oil/water separation apparatus is also set up through equipping the superhydrophobic sponge on a peristaltic pump, realizing the clean-up of oils and organic solvents from water continuously. Together with the facile, easy-to-scale-up and substrate non-selective features of plant polyphenol-inspired chemistry, the superhydrophobic sponge and the surface nano-engineering method would hold great promise for the effective treatment of oil spillages and organic discharges, achieving high sustainability to energy and environment.

Determination of the phytoremediation efficiency of Ricinus communis L. and methane uptake from cadmium and nickel-contaminated soil using spent mushroom substrate.

Spent mushroom substrate (SMS) as an organic amendment to plant production has received increasing attention on soil phytoremediation. However, organic amendments are known to contribute to greenhouse gas (GHG) emission from soils. Castor oil plant has a high biomass production and phytoremediation potential for heavy metal-contaminated soils. In the present study, the roles of SMS on phytoremediation efficiency of castor oil plant (Ricinus communis L.) from cadmium (Cd) and nickel (Ni)-contaminated soils were investigated, and the impact of SMS application on methane emission from the contaminated soil were evaluated. Pot experiments with SMS-amended and unamended contaminated soils were conducted to investigate Cd and Ni accumulation in R. communis and CH4 emission. After growing for 3 months in soils with the addition of Cd (10 mg/kg) and Ni (at rates of 200 and 600 mg/kg), the dry biomass and the concentrations of Cd and Ni in the R. communis were measured, and the mobility factors for Cd and Ni were calculated. To assess methane emission, CH4 fluxes and potential rates of CH4 production and oxidation were measured pre- and post-incubation. SMS addition significantly improved the growth of R. communis and gave 19.15~82.46% more dry weight as compared to the single plant cultivation in the contaminated soils. SMS also increased plant Cd uptake and the total amount of Cd accumulation in R. communis increased by 28.1-152.1%, respectively, in signal Cd treatment and Cd-Ni complexation treatment, as compared to the single plant cultivation. The high values of mobility factor for Cd in single plant cultivation and co-application of SMS and R. communis pointed to the potential of R. communis to the Cd mobilization from the contaminated soils. Moreover, the addition of SMS tended to stimulate CH4 uptake that the average increases in CH4 uptake rate were 3.84-fold (in controls) and 2.91-fold (in single Cd treated soils) by the co-application of SMS and R. communis as compared to the single plant cultivation. The results suggested that the application of SMS could improve the growth of R. communis in Cd and Ni-contaminated soil, enhance heavy metal bioaccumulation, and stimulate soil CH4 uptake. Therefore, SMS might be useful for enhancing phytoremediation of heavy metals and mitigate CH4 emission from the contaminated soil. In addition, results in the study implied that implementing carefully designed management strategies (e.g., application of organic residues) during contaminated soil remediation is a promising solution for agricultural waste management and soil phytoremediation.

Functionalized three-dimensional graphene sponges for highly efficient crude and diesel oil adsorption.

Modified Hummer's method has been used in this study to synthesize graphene oxide (GO) solution that was utilized for the fabrication of three-dimensional (3D) graphene sponges and their subsequent functionalization through a low-cost and facile vapor-based surface enhancement approach. The functionalized 3D-graphene sponge is an excellent absorbent, which can remove more than 3300 wt.% of crude oil (calculated with respect to the original sorbent mass). The functionalization of the obtained graphene sponges with trichloro (1H,1H,2H,2H-perfluorooctyl)silane enhanced their wettability properties due to the super-hydrophobic nature of the resulting materials characterized by the contact angles in water greater than 150°. Furthermore, their elastic compression modulus (estimated by conducting a series of compression tests) was about 22.3 kPa. The equilibrium modeling of the oil removal process, which was performed by plotting Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich isotherms, confirmed the properties of the fabricated 3D graphene sponges as exceptional absorbents for crude and diesel oil, which could be attributed to the oleophilic nature of graphene. Moreover, the obtained 3D graphene sponges could be regenerated via heat treatment, which was conducted to release the adsorbed species. After five adsorption-desorption cycles, the sorption capacity of the produced 3D graphene sponges towards crude oil reached 95% of the initial value.

Bio-inspired Ni2+-polyphenol hydrophilic network to achieve unconventional high-flux nanofiltration membranes for environmental remediation.

A novel Ni2+-polyphenol network was designed as an excellent bio-coating by a one-step strategy to obtain nanofiltration membranes, possessing unconventional high water flux up to 56.1 L m-2 h-1 bar-1 with rose bengal (RB) rejection above 95%. This study provides a facile approach to prepare highly-efficient nanofiltration membranes for wastewater remediation.

Effectiveness of a chemical herder in association with in-situ burning of oil spills in ice-infested water.

The average herded slick thickness, surface distribution and burning efficiency of a light crude oil were studied in ice-infested water to determine the effectiveness of a chemical herder in facilitating the in-situ burning of oil. Experiments were performed in a small scale (1.0m2) and an intermediate scale (19m2) setup with open water and 3/10, 5/10 and 7/10 brash ice coverages. The herded slick thicknesses (3-8mm) were ignitable in each experiment. The presence of ice caused fracturing of the oil during the herding process, which reduced the size of the herded slicks and, as a consequence, their ignitability, which in turn decreased the burning efficiency. Burning efficiencies relative to the ignited fraction of the oil were in the expected range (42-86%). This shows that the herder will be an effective tool for in-situ burning of oil when the ignitability issues due to fracturing of the oil are resolved.

Phytoremediation of palm oil mill secondary effluent (POMSE) by Chrysopogon zizanioides (L.) using artificial neural networks.

Artificial neural networks (ANNs) have been widely used to solve the problems because of their reliable, robust, and salient characteristics in capturing the nonlinear relationships between variables in complex systems. In this study, ANN was applied for modeling of Chemical Oxygen Demand (COD) and biodegradable organic matter (BOD) removal from palm oil mill secondary effluent (POMSE) by vetiver system. The independent variable, including POMSE concentration, vetiver slips density, and removal time, has been considered as input parameters to optimize the network, while the removal percentage of COD and BOD were selected as output. To determine the number of hidden layer nodes, the root mean squared error of testing set was minimized, and the topologies of the algorithms were compared by coefficient of determination and absolute average deviation. The comparison indicated that the quick propagation (QP) algorithm had minimum root mean squared error and absolute average deviation, and maximum coefficient of determination. The importance values of the variables was included vetiver slips density with 42.41%, time with 29.8%, and the POMSE concentration with 27.79%, which showed none of them, is negligible. Results show that the ANN has great potential ability in prediction of COD and BOD removal from POMSE with residual standard error (RSE) of less than 0.45%.

Biodegradation of 2-naphthalensulfonic acid polymers by white-rot fungi: Scale-up into non-sterile packed bed bioreactors.

This paper presents a first scale up under non-sterile conditions of the biodegradation process of 2-naphthalensulfonic acid polymers (NSAP) contained in a petrochemical wastewater by two white-rot fungi (Bjerkandera adusta and Pleurotus ostreatus). The biodegradation experiment was conducted first in flasks and then in packed-bed bioreactors filled with inert and biodegradable carriers (straw), the latter acting as both physical support and carbon source. Reactor inoculated with P. ostreatus attached on straw worked under non-sterile conditions for three months showing 30 ± 5% NSAP degradation. Respirometric tests showed that the fungal treatment was also able to significantly increase the biodegradable fraction of the wastewater COD, which rose from 9% to 40%. It was observed that the fungal degradation of the straw in the bed releases non-biodegradable by-products. Taking into account this contribution to nbCOD, the combined treatment of fungi and activated sludge could theoretically be able to reduce the original COD by up to 73%.

Nylon 6,6 Nonwoven Fabric Separates Oil Contaminates from Oil-in-Water Emulsions.

Industrial oil spills into aquatic environments can have catastrophic environmental effects. First responders to oil spills along the coast of the Gulf of Mexico in the southern United States have used spunbond nylon fabric bags and fences to separate spilled oil and oil waste from contaminated water. Low area mass density spunbond nylon is capable of sorbing more than 16 times its mass in low viscosity crude oil and more than 26 times its mass in higher viscosity gear lube oil. Nylon bags separated more than 95% of gear lube oil contaminate from a 4.5% oil-in-water emulsion. Field testing of spunbond nylon fences by oil spill first responders has demonstrated the ability of this material to contain the oily contaminate while allowing water to flow through. We hypothesize that the effectiveness of nylon as an oil filter is due to the fact that it is both more oleophilic and more hydrophilic than other commonly used oil separation materials. The nylon traps oil droplets within the fabric or on the surface, while water droplets are free to flow through the fabric to the water on the opposite side of the fabric.

A possible method for in situ nitrogen removal in landfills by microbial-pumping-iron behavior.

Nitrogen pollution from landfills needs urgent treatment. A batch experiment was designed to explore the possible in situ nitrogen removal in landfills based on the hypothesis of microbial-pumping-iron behavior, namely anaerobic microbial iron oxidation and reduction. The results confirm that a simultaneous Fe(ii) oxidation, accompanied by nitrate (NO3(-)-N) reduction and dissimilatory Fe(iii) reduction, can happen in aged municipal solid waste (AMSW). This phenomenon can last at least 10 years after landfilling. Organics is an important intermediate medium in that process. The dynamic anaerobic Fe redox cycle has the potential of denitrification without ammonia nitrogen (NH4(+)-N) accumulation. AMSW with deposited ages of 1-3 years is a good choice to enhance this redox cycle behavior coupled with denitrification. Conversely, AMSW with longer deposited ages (8-10 years) has a quicker iron cycle and a smaller NH4(+)-N accumulation. This suggests a possible method for in situ nitrogen removal in landfills.

Startup and long term operation of enhanced biological phosphorus removal in continuous-flow reactor with granules.

The startup and long term operation of enhanced biological phosphorus removal (EBPR) in a continuous-flow reactor (CFR) with granules were investigated in this study. Through reducing the settling time from 9min to 3min gradually, the startup of EBPR in a CFR with granules was successfully realized in 16days. Under continuous-flow operation, the granules with good phosphorus and COD removal performance were stably operated for more than 6months. And the granules were characterized with particle size of around 960µm, loose structure and good settling ability. During the startup phase, polysaccharides (PS) was secreted excessively by microorganisms to resist the influence from the variation of operational mode. Results of relative quantitative PCR indicated that granules dominated by polyphosphate-accumulating organisms (PAOs) were easier accumulated in the CFR because more excellent settling ability was needed in the system.

Influence of nitrogen form on the phytoextraction of cadmium by a newly discovered hyperaccumulator Carpobrotus rossii.

Using hyperaccumulator plants is an important method to remove heavy metals from contaminated land. Carpobrotus rossii, a newly found Cd hyperaccumulator, has shown potential to remediate Cd-contaminated soils. This study examined the effect of nitrogen forms on Cd phytoextraction by C. rossii. The plants were grown for 78 days in an acid soil spiked with 20 mg Cd kg(-1) and supplied with (NH4)2SO4, Ca(NO3)2, urea, and chicken manure as nitrogen (N) fertilizers. Nitrification inhibitor dicyandiamide (DCD) was applied to maintain the ammonium (NH4(+)) form. Nitrogen fertilization increased shoot biomass but decreased root biomass with the highest shoot biomass occurring in the manure treatment. Compared to the no-N control, urea application did not affect shoot Cd concentration, but increased Cd content by 17% due to shoot biomass increase. Chicken manure significantly decreased CaCl2-extractable Cd in soil, and the Cd concentration and total Cd uptake in the plant. Rhizosphere pH was the highest in the manure treatment and the lowest in the NH4(+) treatments. The manure and nitrate (NO3(-)) treatments tended to have higher rhizosphere pH than their respective bulk soil pH, whereas the opposite was observed for urea and NH4(+) treatments. Furthermore, the concentrations of extractable Cd in soil and Cd in the plant correlated negatively with rhizosphere pH. The study concludes that urea significantly enhanced the Cd phytoaccumulation by C. rossii while chicken manure decreased Cd availability in soil and thus the phytoextraction efficiency.

Optimization of Cadmium (CD(2+)) removal from aqueous solutions by novel biosorbent.

In this research, dead leaves of a common ornamental plant, Dracaena draca known also as dragon tree was used as a biosorbent for the removal of Cadmium (Cd(2+)) from aqueous solutions using a full 2(3) factorial experimental design. Three factors were investigated at two different levels, metal ion concentration (X = 10 and 100 ppm), hydrogen ion concentration (Ph = 2 and 7) and biomass dose (BD = 0.1 and 0.5g). Experiments were carried out in duplicates with 50 ml of Cd(2+) solutions at room temperature. When comparing observed values (experimental) with calculated values (model), they were set closely together that allowed suggesting a normal distribution where (R(2) = 0.9938). A characterization of the biosorbent was done by pHzpc and SEM-EDAX. Results also showed that the most significant effect for Cd(2+) biosorption was ascribed to (X). The interaction effects of (pH BD) and (X pH) were found to have significant influence on Cd(2+) removal efficiency. The highest Cd(2+) removal percentage attained by 79.60% at X = 10 ppm, pH = 7 and BD = 0.5g. The reusability of the biosorbent was tested in three desorption cycles and the regeneration efficiency was above 99.7%.

PCDD/F and PCB water column partitioning examination using natural organic matter and black carbon partition coefficient models.

A 9-year water dataset from the Houston Ship Channel (HSC) was analyzed to understand partitioning in polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/Fs). Total PCBs had more mass as dissolved (74%) whereas total PCDD/Fs did not (11%). Generally, the limited number of PCDD/Fs (only 2378 substituted) explained these differences though differences in chemical behavior beyond log K ow also likely influence partitioning. The particular fractionation seen in the HSC also seemed related to a wide variation in particulate organic carbon (POC)/dissolved organic carbon (DOC) ratio (0.42-180%). Published and unaltered linear free energy and linear solvation energy relationships for DOC, POC, and particulate black carbon (BC) resulted in predictions that were at best 27% (PCB) and 25% root-mean-square error (RMSE) (PCDD/F) partition fraction compared to observed (using estimated BC/POC fractions of 10 and 25%, respectively). These results show, at least in light of the uncertainties in this data (e.g., precise fraction of BC), that a 25% accuracy in model prediction of operationally dissolved or suspended fraction for any one PCB or PCDD/F congener is the best prediction that may be expected. It is therefore recommended that site-specific data be used to calibrate most any water column-partitioning model if it is to be expected to describe what actually occurs in field conditions.

Sulfur crosslinks from thermal degradation of chitosan dithiocarbamate derivatives and thermodynamic study for sorption of copper and cadmium from aqueous system.

Pristine chitosan beads were modified with sulfur (S)-containing functional groups to produce thiolated chitosan beads (ETB), thereby increasing S donor ligands and crosslinks. The effect of temperature, heating time, carbon disulfide (CS2)/chitosan ratio, and pH on total S content of ETB was examined using Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The total S content of ETB increased with increasing CS2/chitosan ratio and decreased with decreasing pH and increasing temperature (>60 °C) and heating time (at 60 °C). Spectroscopic analyses revealed the presence of thiol (-SH)/thione, disulfide (-S-S-), and sulfonate groups in ETB. The thiolation mechanism involves decomposition of dithiocarbamate groups, thereby forming thiourea crosslinks and trithiocarbonate, resulting in -SH oxidation to produce -S-S- crosslinks. The partially formed ETB crosslinks contribute to its acid stability and are thermodynamically feasible in adsorbing Cd and Cu. The S-containing functional groups added to chitinous wastes act as sorbents for metal remediation from acidic environments.