Hybridization of the natural antibiotic, cinnamic acid, with layered double hydroxides (LDH) as green pesticide

Background, aim, and scope  

Heavy application of highly toxic synthetic pesticides has been committed to protect crops against insects and diseases, which have brought about serious environmental problems. Thus, an inevitable and fundamental issue has been how to protect crops without harmful effects on nature. As a fascinating nature-compatible approach, we have attempted to hybridize soil-compatible layered double hydroxides (LDHs) with natural antibiotic substances. Only a few of natural antibiotic substances are available for pest control mainly because of their inherent properties such as easy degradability, high minimum inhibition concentration for practical application, and often extremely low availability, whereas LDHs exhibit unique properties such as anion exchange capacity, acid lability, and high affinity to ubiquitous carbonate ion which make them an excellent inorganic matrix to carry labile biomolecules in soils. This study focuses on the behavior of cinnamate–LDH hybrid in soils and the evaluation of its potentials as a green pesticide.     

Phosphorus concentrations in soil and subsurface water: a field study among cropland and riparian buffers

Riparian buffers can be effective at removing phosphorus (P) in overland flow, but their influence on subsurface P loading is not well known. Phosphorus concentrations in the soil, soil solution, and shallow ground water of 16 paired cropland-buffer plots were characterized during 2004 and 2005. The sites were located at two private dairy farms in Central New York on silt and gravelly silt loams (Aeric Endoaqualfs, Fluvaquentic Endoaquepts, Fluvaquentic Eutrudepts, Glossaquic Hapludalfs, and Glossic Hapludalfs). It was hypothesized that P availability (sodium acetate extractable-P) and soil-landscape variability would affect P release to the soil solution and shallow ground water. Results showed that P availability tended to be greater in crop fields relative to paired buffer plots. Soil P was a good indicator of soil solution dissolved (<0.45 microm) molybdate-reactive P (DRP) concentrations among plots, but was not independently effective at predicting ground water DRP concentrations. Mean ground water DRP in corn fields ranged from < or =20 to 80 microg L(-1), with lower concentrations in hay and buffer plots. More imperfectly drained crop fields and buffers tended to have greater average DRP, particulate (> or =0.45 microm) reactive P (PRP), and dissolved unreactive P (DUP) concentrations in ground water. Soil organic matter and 50-cm depth soil solution DRP in buffers jointly explained 75% of the average buffer ground water DRP variability. Results suggest that buffers were relatively effective at reducing soil solution and shallow ground water DRP concentrations, but their impact on particulate and organic P in ground water was less clear.     

Single-well, gas-sparging tests for evaluating the in situ aerobic cometabolism of cis-1,2-dichloroethene and trichloroethene

This study developed single-well, gas-sparging tests for assessing the feasibility of in situ aerobic cometabolism of trichloroethene (TCE) and cis-1,2-dichloroethene (cis-DCE) using propane and methane as growth substrates. Tests were performed in groundwater contaminated with TCE (100-400 microg l(-1)) and cis-DCE (20-60 microg l(-1)). A series of gas-sparging tests was performed by first sparging ("bubbling") gas mixtures in a well fitted with a "straddle" packer and then periodically sampling groundwater from the same well to develop concentration profiles and to estimate transformation rate coefficients. Evidence that gas-sparging of propane (or methane) and oxygen had stimulated organisms expressing a propane (or methane) monooxygenase enzyme system and the capability to transform TCE and cis-DCE included: (1) the transformation of sparged ethylene and propylene to their corresponding cometabolic by-products, ethylene oxide and propylene oxide, (2) the transformation of both cis-DCE and TCE in the propane-sparged well, (3) the transformation of cis-DCE in the methane-sparged well, and (4) the inhibition of ethylene and propylene transformations in the presence of acetylene, a known monooxygenase inactivator. At a well sparged with propane, first-order rate coefficients for propane utilization and ethylene and propylene transformation were similar, ranging from 0.007 to 0.010 h(-1). At the well sparged with methane, the propylene first-order transformation rate coefficient was 0.028 h(-1), a factor of 1.8 and 1.6 greater than methane and ethylene, respectively. The results demonstrated that gas-sparging tests are a rapid, low-cost means of assessing the potential for the in situ aerobic cometabolism of cis-DCE and TCE.     

Cyanide generation during preservation of chlorinated wastewater effluent samples for total cyanide analysis.

Dechlorinating agents and pH adjustment are often used to preserve wastewater samples for cyanide analysis. The effects of four approved preservation protocols on the results of the total cyanide analysis of effluents from four water reclamation plants were examined. The results differed widely, and a clear pattern emerged. Immediate analysis without pH adjustment generally gave total cyanide concentrations below the reporting limit of 5 microg/L, irrespective of the dechlorinating agents used. When the pH was adjusted to > or =12, a slight increase in the measured total cyanide concentration was observed when thiosulfate was used to dechlorinate the samples, and a significant increase (>10 microg/L) was observed when arsenite was used as the dechlorinating agent. These results provide evidence that approved preservation protocols may give rise to cyanide formation in chlorinated wastewater effluent matrices.     

Solidification and recycling of incinerator bottom ash through the addition of colloidal silica (SiO2) solution

The possibility of using incinerator bottom ash as a substitute for natural aggregates was investigated. Rough, porous surface of bottom ash, which diminishes the strength of solidified products, was improved by colloidal silica solution. As a result, a significant increase of mechanical strength was accomplished by a slight amount of silica (<1 wt% to total). Moreover, pozzolanic reaction was induced in initial cement hydration due to the nano-particle size of about 20 nm in colloidal silica solution. Cylindrical specimens and bricks were prepared from bottom ash added to a colloidal silica (SiO2) solution and cement, and then their compressive strengths were evaluated. Cylindrical specimens showed an increase of approximately 60% in compressive strength when colloidal solution containing 4 wt% silica particles was sprayed onto the bottom ash. The strength of bricks containing colloidal silica was in excess of 20 MPa, which meets the requirement of construction materials. Results of leaching tests based on Toxicity Characteristic Leaching Procedure (TCLP) proved that the solidified bottom ash possessed good chemical stability.     

Membrane introduction/laser photoionization time-of-flight mass spectrometry

Two-photon resonance enhanced multiphoton ionization (REMPI) has been shown to be a unique ionization method for mass spectrometry, exhibiting both high sensitivity and chemical selectivity. Because REMPI is a gas-phase method, its applications have been limited either to direct analysis of vapor phase samples, or in conjunction with an initial laser desorption or other vaporization step. We describe here for the first time a combination of membrane introduction mass spectrometry (MIMS) and REMPI with time-of-flight mass spectrometry (TOF-MS), which allows for the direct analysis of trace amounts of organic compounds in water samples. The objective of our research was the detection of very low levels of aromatic contaminants, particularly benzene, toluene, and xylene (BTX), in aqueous solutions without interference due to the water. We have measured limits of detection (LOD) for selected aromatics in water below 1 part-per-trillion with an averaging time of less than 10 s using a continuous sample flow.     

Excess copper induced physiological and proteomic changes in germinating rice seeds

Copper is an essential micronutrient for plants. Present at a high concentration in soil, copper is also regarded as a major toxicant to plant cells due to its potential inhibitory effects against many physiological and biochemical processes. The interference of germination-related proteins by heavy metals has not been well documented at the proteomic level. In the current study, physiological, biochemical and proteomic changes of germinating rice seeds were investigated under copper stress. Germination rate, shoot elongation, plant biomass, and water content were decreased, whereas accumulation of copper and TBARS content in seeds were increased significantly with increasing copper concentrations from 0.2mM to 1.5mM followed by germination. The SDS-PAGE showed the preliminary changes in the polypeptides patterns under copper stress. Protein profiles analyzed by two-dimensional electrophoresis (2-DE) revealed that 25 protein spots were differentially expressed in copper-treated samples. Among them, 18 protein spots were up-regulated and 7 protein spots were down-regulated. These differentially displayed proteins were identified by MALDI-TOF mass spectrometry. The up-regulation of some antioxidant and stress-related proteins such as glyoxalase I, peroxiredoxin, aldose reductase, and some regulatory proteins such as DnaK-type molecular chaperone, UlpI protease, and receptor-like kinase clearly indicated that excess copper generates oxidative stress that might be disruptive to other important metabolic processes. Moreover, down-regulation of key metabolic enzymes like alpha-amylase or enolase revealed that the inhibition of seed germinations after exposure to excess copper not only affects starvation in water uptake by seeds but also results in failure in the reserve mobilization processes. These results indicate a good correlation between the physiological and biochemical changes in germinating rice seeds exposed to excess copper.     

Photodecomposition of o-cresol by UV-LED/TiO2 process with controlled periodic illumination

This study investigated the effect of controlled periodic illumination on the photonic efficiency and temporal decomposition behavior of o-cresol by UV/TiO2 process in a slurry reactor using light emitting diodes as the light source. Based on the same UV light intensity of 6.7 W m(-2), the calculated photonic efficiencies increased from 1.5% to 6.3% with the decreasing duty cycle from 1.0 to 0.1 possibly ascribed to the decreasing electron-hole recombination. Actually, the calculated photonic efficiency under periodic illumination at sufficiently intermittence was inferior to, but approached, those under continuous illumination at equivalent average UV light intensity. The calculated electric energy per order increased from 32 to 37 k W h m(-3)order(-1) for experiments conducted with the increasing duty cycle from 0.1 to 1.0, and the electric energy consumption decreased significantly due to the lower duty cycle and average UV light intensity. The photocatalytic decomposition of o-cresol with the UV-light emitting diodes light could be well modeled by the Langmuir-Hinshelwood kinetic equation.     

Seasonal breeding aggregations in low-density populations of the bathyal echinoid Stylocidaris lineata

Reproduction of bathyal cidaroid sea urchins was studied between 1985 and 1991 with the aid of a manned submersible in the northern Bahamas. During May 1988 and February 1990, discrete, single-species aggregations of Stylocidaris lineata containing 2 to 6 individuals were observed between 510 and 640 m depths. Reproductive conditions of isolated and aggregated individuals were determined histologically. In February, all individuals, regardless of their spatial distribution, contained developing gametes. During the May spawning season, most isolated individuals contained spent gonads with only relict gametes, whereas individuals in discrete aggregations mostly contained ripe gonads with mature or nearly-mature gametes. Aggregations were not observed during the autumn months, when gonads were spent or immature. These data suggest that bathyal cidaroids aggregate for reproduction. An in situ survey during May indicated that pairs of S. lineata are more common than larger clumps, but no more so than predicted by chance. Homosexual and heterosexual pairs occur at the relative frequencies predicted on the basis of sex ratio. We evaluated the need for reproductive aggregation by applying Denny's (1988) model that predicts downstream sperm concentration in a turbulent boundary layer. Flow parameters were measured with dye injected from the submersible, sperm-release rate was estimated in the laboratory, and the relationship between fertilization success and sperm concentration was determined in a laboratory dilution-experiment. The model predicted that, on smooth sandy bottoms at bathyal depths, sperm concentration should remain high enough to fertilize at least some eggs several meters directly downstream from a spawning male. Aggregation may facilitate spawning synchrony, increase gamete encounter probabilities, or cause gametes to be retained at high concentrations near the adults long enough for fertilization to occur.