Health effects of herbicides and its current removal strategies.

The continually expanding global population has necessitated increased food supply production. Thus, agricultural intensification has been required to keep up with food supply demand, resulting in a sharp rise in pesticide use. The pesticide aids in the prevention of potential losses caused by pests, plant pathogens, and weeds, but excessive use over time has accumulated its occurrence in the environment and subsequently rendered it one of the emerging contaminants of concern. This review highlights the sources and classification of herbicides and their fate in the environment, with a special focus on the effects on human health and methods to remove herbicides. The human health impacts discussion was in relation to toxic effects, cell disruption, carcinogenic impacts, negative fertility effects, and neurological impacts. The removal treatments described herein include physicochemical, biological, and chemical treatment approaches, and advanced oxidation processes (AOPs). Also, alternative, green, and sustainable treatment options were discussed to shed insight into effective treatment technologies for herbicides. To conclude, this review serves as a stepping stone to a better environment with herbicides.

Environment impact and bioenergy analysis on the microwave pyrolysis of WAS from food industry: Comparison of CO2 and N2 atmosphere.

The alarming output of waste activated sludge (WAS) from industries requires proper management routes to minimize its impact on the environment during disposal. Pyrolysis is a feasible way of processing and valorizing WAS into higher-value products of alternate use. Despite extensive research into the potential of WAS through pyrolysis, the technology's long-term viability and environmental impact have yet to be fully revealed. In addition, the environmental effects of utilizing different pyrolysis atmosphere (N2 or CO2) has not been studied before, although benefits of CO2 reactivity during pyrolysis have been discovered. This study evaluates the process's environmental impact, carbon footprint, and bioenergy yield when different pyrolysis atmospheres are used. The global warming potential (GWP) for a functional unit of 1 t of dried WAS is 203.81 kg CO2 eq. The heat required during pyrolysis contributes the most (63.7%) towards GWP due to high energy usage, followed by the drying process (23.6%). Transportation contributes the most towards toxicity impact (59.3%) through dust, NOx, NH3 and SO2 emissions. The initial moisture content of raw WAS (65%) greatly impacts overall energy consumption and environmental impact. Pyrolysis in an N2 atmosphere will result in a higher overall bioenergy yield (833 kWh/tonne) and a lower carbon footprint (-1.09 kg CO2/tonne). However, when CO2 was used, the specific energy value within the biochar is higher (22.26 MJ/kg) due to enhanced carbonization. The carbon content of gas derived increased due to higher CO yield. From an energy perspective, the current setup will achieve a net positive bioenergy yield of 561 kW (CO2) and 833 kW (N2), where end products like biochar, bio-oil and gas can be used for power production. Despite the energy-intensive process, microwave pyrolysis has excellent potential to achieve a negative carbon footprint. The biochar used for soil amendment served as a good carbon sink. The utilization of CO2 as carrier gases provides a pathway to utilize anthropogenic CO2, which helps reduce global warming. This work demonstrates microwave pyrolysis as a negative emission, bioenergy-producing approach for WAS disposal and valorization.

Characterization and antiinflammatory properties of fractionated pyroligneous acid from palm kernel shell.

Pyroligneous acid (PA) obtained from slow pyrolysis of palm kernel shell (PKS) has high total phenolic contents and exhibits various biological activities including antioxidant, antibacterial and antifungal. In this study, PA obtained using slow pyrolysis method and fractionated using column chromatography was characterized (chemical and antioxidative properties) and investigated for its cyclooxygenase-2 (COX-2) and 5-lipoxygenase (5-LOX) inhibition activities using the in vitro and in silico approaches. The F9 PA fraction exhibited highest total phenolic content of 181.75 ± 17.0 µg/mL. Fraction F21-25 showed ferric reducing antioxidant power (FRAP) (331.80 ± 4.60 mg TE/g) and IC50 of 18.56 ± 0.01 µg/mL towards COX-2 and 5.25 ± 0.03 µg/mL towards the 5-LOX enzymes, respectively. Molecular docking analysis suggested favourable binding energy for all chemical compounds present in fraction F21-25, notably 1-(2,4,6-trihydroxyphenyl)-2-pentanone, towards both COX-2 (- 6.9 kcal/mol) and 5-LOX (- 6.4 kcal/mol) enzymes. As a conclusion, PA from PKS has the potential to be used as an alternative antioxidant and antiinflammatory agents which is biodegradable and a more sustainable supply of raw materials.

Preparation, characterization, and dye removal study of activated carbon prepared from palm kernel shell.

Palm oil mill wastes (palm kernel shell (PKS)) were used to prepare activated carbons, which were tested in the removal of colorants from water. The adsorbents were prepared by 1-h impregnation of PKS with ZnCl2 as the activating agent (PKS:ZnCl2 mass ratios of 1:1 and 2:1), followed by carbonization in autogenous atmosphere at 500 and 550 °C during 1 h. The characterization of the activated carbons included textural properties (porosity), surface chemistry (functional groups), and surface morphology. The dye removal performance of the different activated carbons was investigated by means of the uptake of methylene blue (MB) in solutions with various initial concentrations (25-400 mg/L of MB) at 30 °C, using a 0.05-g carbon/50-mL solution relationship. The sample prepared with 1:1 PKS:ZnCl2 and carbonized at 550 °C showed the highest MB adsorption capacity (maximum uptake at the equilibrium, q max = 225.3 mg MB / g adsorbent), resulting from its elevated specific surface area (BET, 1058 m2/g) and microporosity (micropore surface area, 721 m2/g). The kinetic experiments showed that removals over 90% of the equilibrium adsorptions were achieved after 4-h contact time in all the cases. The study showed that palm oil mill waste biomass could be used in the preparation of adsorbents efficient in the removal of colorants in wastewaters.

Reactivity of phenolic compounds towards free radicals under in vitro conditions.

The free radical scavenging activity and reducing power of 16 phenolic compounds including four hydroxycinnamic acid derivatives namely ferulic acid, caffeic acid, sinapic acid and p-coumaric acid, benzoic acid and its derivatives namely protocatechuic acid, gallic acid and vanillic acid, benzene derivatives namely vanillin, vanillyl alcohol, veratryl alcohol, veratraldehyde, pyrogallol, guaiacol and two synthetic antioxidants, butylated hydroxy anisole (BHA) and propyl gallate were evaluated using 1,1-Diphenyl-2-picrylhydrazyl radical (DPPH(•)), 2,2'-Azinobis-3- ethylbenzothiazoline-6-sulfonic acid radical (ABTS(+•)), Hydroxyl radical ((•)OH) and Superoxide radical (O2 (•-)) scavenging assays and reduction potential assay. By virtue of their hydrogen donating ability, phenolic compounds with multiple hydroxyl groups such as protocatechuic acid, pyrogallol, caffeic acid, gallic acid and propyl gallate exhibited higher free radical scavenging activity especially against DPPH(•) and O2 (•-). The hydroxylated cinnamates such as ferulic acid and caffeic acid were in general better scavengers than their benzoic acid counter parts such as vanillic acid and protocatechuic acid. All the phenolic compounds tested exhibited more than 85 % scavenging due to the high reactivity of the hydroxyl radical. Phenolic compounds with multiple hydroxyl groups also exhibited high redox potential. Exploring the radical scavenging and reducing properties of antioxidants especially those which are found naturally in plant sources are of great interest due to their protective roles in biological systems.

Optimization of culture conditions for flexirubin production by Chryseobacterium artocarpi CECT 8497 using response surface methodology.

Flexirubins are the unique type of bacterial pigments produced by the bacteria from the genus Chryseobacterium, which are used in the treatment of chronic skin disease, eczema etc. and may serve as a chemotaxonomic marker. Chryseobacterium artocarpi CECT 8497, an yellowish-orange pigment producing strain was investigated for maximum production of pigment by optimizing medium composition employing response surface methodology (RSM). Culture conditions affecting pigment production were optimized statistically in shake flask experiments. Lactose, l-tryptophan and KH2PO4 were the most significant variables affecting pigment production. Box Behnken design (BBD) and RSM analysis were adopted to investigate the interactions between variables and determine the optimal values for maximum pigment production. Evaluation of the experimental results signified that the optimum conditions for maximum production of pigment (521.64 mg/L) in 50 L bioreactor were lactose 11.25 g/L, l-tryptophan 6 g/L and KH2PO4 650 ppm. Production under optimized conditions increased to 7.23 fold comparing to its production prior to optimization. Results of this study showed that statistical optimization of medium composition and their interaction effects enable short listing of the significant factors influencing maximum pigment production from Chryseobacterium artocarpi CECT 8497. In addition, this is the first report optimizing the process parameters for flexirubin type pigment production from Chryseobacterium artocarpi CECT 8497.

Pyroligneous acid-the smoky acidic liquid from plant biomass.

Pyroligneous acid (PA) is a complex highly oxygenated aqueous liquid fraction obtained by the condensation of pyrolysis vapors, which result from the thermochemical breakdown or pyrolysis of plant biomass components such as cellulose, hemicellulose, and lignin. PA produced by the slow pyrolysis of plant biomass is a yellowish brown or dark brown liquid with acidic pH and usually comprises a complex mixture of guaiacols, catechols, syringols, phenols, vanillins, furans, pyrans, carboxaldehydes, hydroxyketones, sugars, alkyl aryl ethers, nitrogenated derivatives, alcohols, acetic acid, and other carboxylic acids. The phenolic components, namely guaiacol, alkyl guaiacols, syringol, and alkyl syringols, contribute to the smoky odor of PA. PA finds application in diverse areas, as antioxidant, antimicrobial, antiinflammatory, plant growth stimulator, coagulant for natural rubber, and termiticidal and pesticidal agent; is a source for valuable chemicals; and imparts a smoky flavor for food.

Chryseobacterium artocarpi sp. nov., isolated from the rhizosphere soil of Artocarpus integer.

A bacterial strain, designated UTM-3(T), isolated from the rhizosphere soil of Artocarpus integer (cempedak) in Malaysia was studied to determine its taxonomic position. Cells were Gram-stain-negative, non-spore-forming rods, devoid of flagella and gliding motility, that formed yellow-pigmented colonies on nutrient agar and contained MK-6 as the predominant menaquinone. Comparative analysis of the 16S rRNA gene sequence of strain UTM-3(T) with those of the most closely related species showed that the strain constituted a distinct phyletic line within the genus Chryseobacterium with the highest sequence similarities to Chryseobacterium lactis NCTC 11390(T), Chryseobacterium viscerum 687B-08(T), Chryseobacterium tructae 1084-08(T), Chryseobacterium arthrosphaerae CC-VM-7(T), Chryseobacterium oncorhynchi 701B-08(T), Chryseobacterium vietnamense GIMN1.005(T), Chryseobacterium bernardetii NCTC 13530(T), Chryseobacterium nakagawai NCTC 13529(T), Chryseobacterium gallinarum LMG 27808(T), Chryseobacterium culicis R4-1A(T), Chryseobacterium flavum CW-E2(T), Chryseobacterium aquifrigidense CW9(T), Chryseobacterium ureilyticum CCUG 52546(T), Chryseobacterium indologenes NBRC 14944(T), Chryseobacterium gleum CCUG 14555(T), Chryseobacterium jejuense JS17-8(T), Chryseobacterium oranimense H8(T) and Chryseobacterium joostei LMG 18212(T). The major whole-cell fatty acids were iso-C15 : 0 and iso-C17 : 1ω9c, followed by summed feature 4 (iso-C15 : 0 2-OH and/or C16 : 1ω7t) and iso-C17 : 0 3-OH, and the polar lipid profile consisted of phosphatidylethanolamine and several unknown lipids. The DNA G+C content strain UTM-3(T) was 34.8 mol%. On the basis of the phenotypic and phylogenetic evidence, it is concluded that the isolate represents a novel species of the genus Chryseobacterium, for which the name Chryseobacterium artocarpi sp. nov. is proposed. The type strain is UTM-3(T) ( = CECT 8497(T) = KCTC 32509(T)).

Isotherm kinetics of Cr(III) removal by non-viable cells of Acinetobacter haemolyticus.

The potential use of non-viable biomass of a Gram negative bacterium i.e. Acinetobacter haemolyticus to remove Cr(III) species from aqueous environment was investigated. Highest Cr(III) removal of 198.80 mg g(-1) was obtained at pH 5, biomass dosage of 15 mg cell dry weight, initial Cr(III) of 100 mg L(-1) and 30 min of contact time. The Langmuir and Freundlich models fit the experimental data (R(2)>0.95) while the kinetic data was best described using the pseudo second-order kinetic model (R(2)>0.99). Cr(III) was successfully recovered from the bacterial biomass using either 1M of CH(3)COOH, HNO(3) or H(2)SO(4) with 90% recovery. TEM and FTIR suggested the involvement of amine, carboxyl, hydroxyl and phosphate groups during the biosorption of Cr(III) onto the cell surface of A. haemolyticus. A. haemolyticus was also capable to remove 79.87 mg g(-1) Cr(III) (around 22.75%) from raw leather tanning wastewater. This study demonstrates the potential of using A. haemolyticus as biosorbent to remove Cr(III) from both synthetic and industrial wastewater.

Bacterial reduction of Cr(VI) at technical scale--the Malaysian experience.

The bacterial reduction of Cr(VI) from industrial wastewater was evaluated using a 2.0-m(3) bioreactor. Liquid pineapple waste was used as a nutrient for the biofilm community formed inside the bioreactor. The use of rubber wood sawdust as packing material was able to immobilize more than 10(6) CFU mL(-1) of Acinetobacter haemolyticus cells after 3 days of contact time. Complete reduction of 15-240 mg L(-1) of Cr(VI) was achieved even after 3 months of bioreactor operation. Cr(VI) was not detected in the final effluent fraction indicating complete removal of Cr from solution from the flocculation/coagulation step and the unlikely re-oxidation of Cr(III) into Cr(VI). Impatiens balsamina L. and Gomphrena globosa L. showed better growth in the presence of soil-sludge mixture compared to Coleus scutellarioides (L.) Benth. Significant amounts of Cr accumulated at different sections of the plants indicate its potential application in Cr phytoremediation effort. The bacterial-based system was also determined not to be detrimental to human health based on the low levels of Cr detected in the hair and nail samples of the plant operators. Thus, it can be said that bacterial-based Cr(VI) treatment system is a feasible alternative to the conventional system especially for lower Cr(VI) concentrations, where sludge generated can be used as growth supplement for ornamental plant as well as not detrimental to the health of the workers.

Production and characterization of violacein by locally isolated Chromobacterium violaceum grown in agricultural wastes.

The present work highlighted the production of violacein by the locally isolated Chromobacterium violaceum (GenBank accession no. HM132057) in various agricultural waste materials (sugarcane bagasse, solid pineapple waste, molasses, brown sugar), as an alternative to the conventional rich medium. The highest yield for pigment production (0.82 g L⁻¹) was obtained using free cells when grown in 3 g of sugarcane bagasse supplemented with 10% (v/v) of L-tryptophan. A much lower yield (0.15 g L⁻¹) was obtained when the cells were grown either in rich medium (nutrient broth) or immobilized onto sugarcane bagasse. Violacein showed similar chemical properties as other natural pigments based on the UV-Vis, Fourier transform infrared spectroscopy, thin-layer chromatography, nuclear magnetic resonance, and mass spectrometry analysis. The pigment is highly soluble in acetone and methanol, insoluble in water or non-polar organic solvents, and showed good stability between pH 5-9, 25-100 °C, in the presence of light metal ions and oxidant such as H2O2. However, violacein would be slowly degraded upon exposure to light. This is the first report on the use of cheap and easily available agricultural wastes as growth medium for violacein-producing C. violaceum.

Pilot-scale removal of chromium from industrial wastewater using the ChromeBac system.

The enzymatic reduction of Cr(VI) to Cr(III) by Cr(VI) resistant bacteria followed by chemical precipitation constitutes the ChromeBac system. Acinetobacter haemolyticus was immobilized onto carrier material inside a 0.2m(3) bioreactor. Neutralized electroplating wastewater with Cr(VI) concentration of 17-81 mg L(-1) was fed into the bioreactor (0.11-0.33 m(3)h(-1)). Complete Cr(VI) reduction to Cr(III) was obtained immediately after the start of bioreactor operation. Together with the flocculation, coagulation and filtration, outflow concentration of less than 0.02 mg Cr(VI)L(-1) and 1mg total CrL(-1) were always obtained. Performance of the bioreactor was not affected by fluctuations in pH (6.2-8.4), Cr(VI) (17-81 mg L(-1)), nutrient (liquid pineapple waste, 1-20%v/v) and temperature (30-38 degrees C). Standby periods of up to 10 days can be tolerated without loss in activity. A robust yet effective biotechnology to remove chromium from wastewater is thus demonstrated.

Biological detoxification of Cr(VI) using wood-husk immobilized Acinetobacter haemolyticus.

Acinetobacter haemolyticus, a Gram-negative aerobic locally isolated bacterium, immobilized on wood-husk showed the ability to detoxify Cr(VI) to Cr(III). Wood-husk, a natural cellulose-based support material, packed in an upward-flow column was used as support material for bacterial attachment. Around 97% of the Cr(VI) in wastewater containing 15 mg L(-1) of Cr(VI) was reduced at a flow rate of 8.0 mL min(-1). The wastewater containing Cr(VI) was added with liquid pineapple wastewater as nutrient source for the bacteria. Electron microscopic examinations of the wood-husk after 42 days of column operation showed gradual colonization of the wood-husk by bacterial biofilm. The use of 0.1% (v/v) formaldehyde as a disinfecting agent inhibited growth of bacteria present in the final wastewater discharge. This finding is important in view of the ethical code regarding possible introduction of exogenous bacterial species into the environment.

Hexavalent chromium reduction by Acinetobacter haemolyticus isolated from heavy-metal contaminated wastewater.

Possible application of a locally isolated environmental isolate, Acinetobacter haemolyticus to remediate Cr(VI) contamination in water system was demonstrated. Cr(VI) reduction by A. haemolyticus seems to favour the lower concentrations (10-30 mg/L). However, incomplete Cr(VI) reduction occurred at 70-100 mg/L Cr(VI). Initial specific reduction rate increased with Cr(VI) concentrations. Cr(VI) reduction was not affected by 1 or 10 mM sodium azide (metabolic inhibitor), 10 mM of PO(4)3-, SO4(2-), SO(3)2-, NO3- or 30 mg/L of Pb(II), Zn(II), Cd(II) ions. However, heat treatment caused significant dropped in Cr(VI) reduction to less than 20% only. A. haemolyticus cells loses its shape and size after exposure to 10 and 50 mg Cr(VI)/L as revealed from TEM examination. The presence of electron-dense particles in the cytoplasmic region of the bacteria suggested deposition of chromium in the cells.