The conversion of chicken manure to biooil by fast pyrolysis I. Analyses of chicken manure,biooils and char by 13C and 1H NMR and FTIR spectrophotometry

Fast pyrolysis of chicken manure produced two biooils (Fractions I and II) and a residual char. All four materials were analyzed by chemical methods, ¹³C and 1H Nuclear Magnetic Resonance Spectrometry (¹³C and 1H NMR), and Fourier Transform Infrared Spectrosphotometry (FTIR). The char showed the highest C content and the highest aromaticity. Of the two biooils Fraction II was higher in C, yield and calorific value but lower in N than Fraction I. The S and ash content of the two biooil fractions were low. The Cross Polarization Magic Angle Spinning (CP-MAS) ¹³C NMR spectrum of the initial chicken manure showed it to be rich in cellulose, which was a major component of sawdust used as bedding material. Nuclear Magnetic Resonance (NMR) spectra of the two biooils indicated that Fraction I was less aromatic than Fraction II. Among the aromatics in the two biooils, we were able to tentatively identify N-heterocyclics like indoles, pyridines, and pyrazines. FTIR spectra were generally in agreement with the NMR data. FTIR spectra of both biooils showed the presence of both primary and secondary amides and primary amines as well as N-heterocyclics such as pyridines, quinolines, and pyrimidines. The FTIR spectrum of the char resembled that of the initial chicken manure except that the concentration of carbohydrates was lower.     

Impact of redox conditions on metolachlor and metribuzin degradation in mississippi flood plain soils

Abstract

The effect of soil redox conditions on the degradation of metolachlor and metribuzin in two Mississippi soils (Forrestdale silty clay loam and Loring silt loam) were examined in the laboratory. Herbicides were added to soil in microcosms and incubated either under oxidized (aerobic) or reduced (anaerobic) conditions. Metolachlor and metribuzin degradation under aerobic condition in the Forrestdale soil proceeded at rates of 8.83 ngd^‐1 and 25 ngd^‐1, respectively. Anaerobic degradation rates for the two herbicides in the Forestdale soil were 8.44 ngd^‐1 and 32.5 ngd^‐1, respectively. Degradation rates for the Loring soil under aerobic condition were 24.8 ngd^‐1 and 12.0 ngd^‐1 for metolachlor and metribuzin, respectively. Metolachlor and metribuzin degradation rates under anaerobic conditions in the Loring soil were 20.9 ngd^‐1 and 5.35 ngd^‐1. Metribuzin degraded faster (12.0 ngd^‐1) in the Loring soil under aerobic conditions as compared to anaerobic conditions (5.35 ngd^‐1).     

A two-generational reproductive toxicity study of zinc in rats

A two-generation reproductive toxicity study of zinc chloride (ZnCl₂) was conducted in rats. F_o male and female rats were administered 0.00 (control), 7.50 (low), 15.00 (mid) and 30.00 (high) mg/kg/day of ZnCl₂. Selected F₁ male and female rats were exposed to the same doses received by their parents (F_o). Exposure of F₀ parental rats to ZnCl₂ showed significant reduction in fertility, viability (days 0 and 4), and the body weight of F₁ pups from the high-dose group but caused no effects on litter size, weaning index, and sex ratio. Similarly, the continued exposure of F₁ parental rats to ZnCl₂ also reduced fertility, liter size, viability (day 0), and the body weight of F₂ pups within the high-dose group but caused no effects on weaning index and sex ratio. Exposure of ZnCl₂ to F₀ and F₁ parental males resulted in a significant reduction in their body weights, and the F₀ and F₁ parental females did not show any significant difference in their body weights compared to their control groups. However, the postpartum dam weights of both F₀ and F₁ female rats were significantly reduced compared to their controls. Exposure of ZnCl₂ to F_o and F₁ generation parental rats did not produce any significant change of their clinical signs as well as their clinical pathology parameters, except the alkaline phosphotase (ALK) level, which showed an upward trend in both sexes of both generations. Exposure of ZnCl₂ to F₀ rats resulted in a reduction of brain, liver, kidney, spleen and seminal vesicles weights of males and in the spleen and uterus of females. Similarly, exposure of F₁ rats to ZnCl₂ also resulted in reduction of brain, liver, kidney, adrenal, spleen, prostate and seminal vesicles weights of males and in spleen and uterus of females. ZnCl₂ exposure resulted in grossly observed gastro-intestianla (GI) tract, lymphoreticular/hematopoietic, and reproductive tract lesions in parental rats in both generations. Reduced body fat was also recorded in F₁ parental rats.     

Evaluation and validation of two different chromatographic methods (HPLC and LC-MS/MS) for the determination and confirmation of ochratoxin A in pig tissues

This study was undertaken to compare two different analytical methods for the determination and confirmation of ochratoxin A (OTA) in blood serum, kidney and liver of pigs. Sample clean-up was based on liquid-liquid phase extraction. The detection of OTA was accomplished with high-performance liquid chromatography (HPLC) combined either with fluorescence detection (FL) or electro spray ionization (ESI+) tandem mass spectrometry (MS–MS). Comparative method evaluation was based on the investigation of 90 samples of blood serum, kidney and liver per animal originating from different regions of Serbia. The analytical results are discussed in view of the respective method validation data and the corresponding experimental protocols. In general, analytical data obtained with (LC–MS–MS) liquid chromatography electro spray tandem mass spectro metry detection offered comparable good results at the sub-ppb concentration level. The results indicate that the liquid chromatography electro spray tandem mass spectrometric (LC-MS/MS) method was more specific and sensitive for the analysis and confirmation of ochratoxin A in pig tissues then high pressure liquid chromatography (HPLC) method after methylation of OTA.     

Metolachlor and chlorothalonil dissipation in gypsum-amended soil

This work focused on the interactive effects of the fungicide chlorothalonil (2,3,4,6-tetrachloro-1,3-benzendicarbonitrile) and gypsum on the persistence of the soil-residual herbicide metolachlor (2-chloro-N-(6-ethyl-o-tolyl)-N-[(1RS)-2-methoxy-1-methylethyl]acetamide). Gypsum application was included due to its widespread use on peanut (Arachis hypogaea). Both agricultural grade gypsum and reagent CaSO₄-2H₂O were tested. A laboratory soil incubation was conducted to evaluate interactive effects. Results indicated 1.5X greater metolachlor half-life (DT₅₀) in soil amended with chlorothalonil (37 d) as compared to control soil (25 d). The two gypsum sources alone increased metolachlor DT₅₀ to about 32 d and with the combination of chlorothalonil and gypsum, DT50 was 50 d, 2-fold greater than the control. Chlorothalonil dissipation was rapid (DT₅₀ < 4d). A possible explanation for metolachlor dissipation kinetics is a build-up of the chlorothalonil intermediate (4-hydroxychlorothalonil) which limited soil microbial activity and depleted glutathione S-transferase (GST) from chlorothalonil detoxification. Further information related to gypsum impacts is needed. Results confirm previous reports of chlorothalonil impeding metolachlor dissipation and showed the gypsum application extended persistence even longer. Farming practices, such as reducing metolachlor application rates, may need to be adjusted for peanut cropping systems where chlorothalonil and gypsum are used.     

Mitigation of odor causing emissions—Bench-scale investigation

Emissions of malodors are considered to be the greatest threat to the compost industry. In work presented here, several simple odor mitigation alternatives were investigated for their effectiveness in preventing the release of common odorants, such as terpenes, ammonia, and reduced sulfur compounds. The mitigation methods studied included the use of a blanket of finished compost, compost amendment mixed within the feedstock, odor neutralizing agents (ONAs), and oxygen release compounds (ORCs). Among the mitigation alternatives investigated in this study, the use of finished compost as a blanket and finished compost as an amendment yielded the most conclusive and significant results. Both of these alternatives yielded a substantial emission reduction for terpenes, ammonia, and reduced sulfur compounds. The application of finished compost blanket resulted in up to 95% reduction of terpene and 25% reduction of ammonia emissions. Blending the feedstock with finished compost also provided substantial reduction of terpene emissions ranging from 73.6 to 93.1% at the 24% blending ratio, and up to 85% ammonia reduction a the 35% blending ratio. Use of finished compost also provided 75% lower reduced sulfur compound emissions at the 12% blending ratio. Misting and application of odor neutralizing agents did not result in any consistent reduction in emissions for any of the odorous compounds tested.

Implications The odor emissions from composting are often considered to be the biggest threat to composting facilities. Because most facilities cannot afford enclosures and contained composting vessels, there is a need to inexpensively and effectively control the odor emissions from composting facilities. The findings of this research can lead the way for efforts to control odor easily and cost effectively. In fact, the application of a compost blanket for odor control is already gaining acceptance by the composting industry.     

In Situ Determination of the Rate of Unassisted Degradation of Saturated-Zone Hydrocarbon Contamination

Abstract

A method to measure the in situ degradation rate of dissolved hydrocarbon contamination has been developed and applied at two locations at a field site. The method uses the rates of downward diffusion of oxygen and upward diffusion of carbon dioxide through the unsaturated zone, as calculated from vertical soil-gas concentration gradients, combined with stoichiometry to obtain two degradation rates in hydrocarbon mass per water table surface area per time. Values of 0.385 gram per m² per day and 0.52 gram per m² per day (based upon oxygen data) and 0.056 gram per m² per day and 0.12 gram per m² per day (based upon carbon dioxide data) were calculated at a field site with dissolved fuel contamination. This result of lower values from ground-air carbon dioxide concentrations is consistent with a significant fraction of the carbon dioxide produced being lost to the aqueous phase. Based upon a single-stage equilibrium phase-transfer model, gas/water volume ratios of 0.02 and 0.2 for the capillary fringe were calculated. Groundwater carbon dioxide fugacities and soil-gas carbon dioxide concentrations were used at the two locations and a third to determine whether the source of elevated soil carbon dioxide concentrations were unsaturated-zone hydrocarbon degradation or a saturated-zone process. This technique has potential applicability in setting risk-based remedial criteria and in allowing inclusion of the contribution of in situ degradation in remedial design. This can result in major remedial cost savings.     

A real-time monitoring and assessment method for calculation of total amounts of indoor air pollutants emitted in subway stations

Subway systems are considered as main public transportation facility in developed countries. Time spent by people in indoors, such as underground spaces, subway stations, and indoor buildings, has gradually increased in the recent past. Especially, operators or old persons who stay in indoor environments more than 15 hr per day usually influenced a greater extent by indoor air pollutants. Hence, regulations on indoor air pollutants are needed to ensure good health of people. Therefore, in this study, a new cumulative calculation method for the estimation of total amounts of indoor air pollutants emitted inside the subway station is proposed by taking cumulative amounts of indoor air pollutants based on integration concept. Minimum concentration of individual air pollutants which naturally exist in indoor space is referred as base concentration of air pollutants and can be found from the data collected. After subtracting the value of base concentration from data point of each data set of indoor air pollutant, the primary quantity of emitted air pollutant is calculated. After integration is carried out with these values, adding the base concentration to the integration quantity gives the total amount of indoor air pollutant emitted. Moreover, the values of new index for cumulative indoor air quality obtained for 1 day are calculated using the values of cumulative air quality index (CAI). Cumulative comprehensive indoor air quality index (CCIAI) is also proposed to compare the values of cumulative concentrations of indoor air pollutants. From the results, it is clear that the cumulative assessment approach of indoor air quality (IAQ) is useful for monitoring the values of total amounts of indoor air pollutants emitted, in case of exposure to indoor air pollutants for a long time. Also, the values of CCIAI are influenced more by the values of concentration of NO₂, which is released due to the use of air conditioners and combustion of the fuel. The results obtained in this study confirm that the proposed method can be applied to monitor total amounts of indoor air pollutants emitted, inside apartments and hospitals as well.

Implications: Nowadays, subway systems are considered as main public transportation facility in developed countries. Time spent by people in indoors, such as underground spaces, subway stations, and indoor buildings, has gradually increased in the recent past. Especially, operators or old persons who stay in the indoor environments more than 15 hr per day usually influenced a greater extent by indoor air pollutants. Hence, regulations on indoor air pollutants are needed to ensure good health of people. Therefore, this paper presents a new methodology for monitoring and assessing total amounts of indoor air pollutants emitted inside underground spaces and subway stations. A new methodology for the calculation of cumulative amounts of indoor air pollutants based on integration concept is proposed. The results suggest that the cumulative assessment approach of IAQ is useful for monitoring the values of total amounts of indoor air pollutants, if indoor air pollutants accumulated for a long time, especially NO₂ pollutants. The results obtained here confirm that the proposed method can be applied to monitor total amounts of indoor air pollutants emitted, inside apartments and hospitals as well.