Emission factor of exhaust gas constituents during the pyrolysis of zinc chloride immersed biosolid

Pyrolysis enables ZnCl₂ immersed biosolid to be reused, but some hazardous air pollutants are emitted during this process. Physical characteristics of biosolid adsorbents were investigated in this work. In addition, the constituents of pyrolytic exhaust were determined to evaluate the exhaust characteristics. Results indicated that the pyrolytic temperature was higher than 500 °C, the specific surface area was >900 m²/g, and the total pore volume was as much as 0.8 cm³/g at 600 °C. For non-ZnCl₂ immersed biosolid pyrolytic exhaust, VOC emission factors increased from 0.677 to 3.170 mg-VOCs/g-biosolid with the pyrolytic temperature increase from 400 to 700 °C, and chlorinated VOCs and oxygenated VOCs were the dominant fraction of VOC groups. VOC emission factors increased about three to seven times, ranging from 1.813 to 21.448 mg/g for pyrolytic temperatures at 400–700 °C, corresponding to the mass ratio of ZnCl₂ and biosolid ranging from 0.25–2.5.     

Effect of Fractionation and Pyrolysis on Fuel Properties of Poultry Litter

Abstract

Raw poultry litter has certain drawbacks for energy production such as high ash and moisture content, a corrosive nature, and low heating values. A combined solution to utilization of raw poultry litter may involve fractionation and pyrolysis. Fractionation divides poultry litter into a fine, nutrient-rich fraction and a coarse, carbon-dense fraction. Pyrolysis of the coarse fraction would remove the corrosive volatiles as bio-oil, leaving clean char. This paper presents the effect of fractionation and pyrolysis process parameters on the calorific value of char and on the characterization of bio-oil. Poultry litter samples collected from three commercial poultry farms were divided into 10 treatments that included 2 controls (raw poultry litter and its coarse fraction having particle size greater than 0.85 mm) and 8 other treatments that were combinations of three factors: type (raw poultry litter or its coarse fraction), heating rate (30 or 10 °C/min), and pyrolysis temperature (300 or 500 °C). After the screening process, the poultry litter samples were dried and pyrolyzed in a batch reactor under nitrogen atmosphere and char and condensate yields were recorded. The condensate was separated into three fractions on the basis of their density: heavy, medium, and light phase. Calorific value and proximate and nutrient analysis were performed for char, condensate, and feedstock. Results show that the char with the highest calorific value (17.39 ± 1.37 MJ/kg) was made from the coarse fraction at 300 °C, which captured 68.71 ± 9.37% of the feedstock energy. The char produced at 300 °C had 42 ± 11 mg/kg arsenic content but no mercury. Almost all of the Al, Ca, Fe, K, Mg, Na, and P remained in the char. The pyrolysis process reduced ammoniacal-nitrogen (NH₄-N) in char by 99.14 ± 0.47% and nitrate-nitrogen (NO₃-N) by 95.79 ± 5.45% at 500 °C.     

Impact of temperature on the dynamics of organic matter and on the soil-to-plant transfer of Cd,Zn and Pb in a contaminated agricultural soil

Predicting the soil-to-plant transfer of metals in the context of global warming has become a major issue for food safety. It requires a better understanding of how the temperature alters the bioavailability of metals in cultivated soils. This study focuses on one agricultural soil contaminated by Cd, Zn and Pb. DGT measurements were performed at 10, 20 and 30 °C to assess how the bioavailability of metals was affected by a rise in soil temperature. A lettuce crop was cultivated in the same conditions to determine if the soil-to-plant transfer of metals increased with a rise in soil temperature. A gradual decline in Cd and Zn bioavailability was observed from 10 to 30 °C, which was attributed to more intense complexation of metals in the pore water at higher temperatures. Together with its aromaticity, the affinity of dissolved organic matter (DOM) for metals was indeed suspected to increase with soil temperature. One main output of the present work is a model which satisfactorily explains the thermal-induced changes in the characteristics of DOM reported in Cornu et al. (Geoderma 162:65–70, 2011) by assuming that the mineralization of initial aliphatic compounds followed a first-order reaction, increased with soil temperature according to the Arrhenius law, and due to a priming effect, led to the appearance of aromatic molecules. The soil-to-plant transfer of Cd and Zn was promoted at higher soil temperatures despite a parallel decrease in Cd and Zn bioavailability. This suggests that plant processes affect the soil-to-plant transfer of Cd and Zn the most when the soil temperature rises.     

17β-Estradiol mineralization under field and laboratory incubations

Mineralization studies of natural steroid hormones (e.g., 17β-estradiol, E2) are performed in environmental incubators, usually under a constant temperature such as 20°C. In this paper, we present a microcosm protocol that quantified the mineralization of E2 in soils under field temperatures. The nine agricultural soils tested had a wide range of soil organic carbon (1.1 to 5.2%) and clay (9 to 57%) contents. The calculated time over which half of the applied E2 was mineralized (E2-½) ranged from 299 to 910 d, and total E2 mineralization at 48 d (E2-TOT48) ranged from 4 to 13%. In subsequent laboratory incubations, the same soils were incubated under a constant temperature of 20°C, as well as under cyclic temperatures of 14.5°C (14 h) and 11.5°C (10h), which was within the temperature extremes observed in the field microcosms. E2-½ ranged from 157 to 686 d at 20°C and from 103 to 608 d at the cyclic temperatures, with the E2-TOT48 ranging from 6 to 21% at 20°C and from 7 to 30% under cyclic temperatures. Despite the overall 6.75°C lower mean temperatures under the cyclic versus constant temperatures, E2 mineralization was stimulated by the temperature cycles in three soils. Regardless of the incubation, the same loamy sand soil always showed larger E2 mineralization than the other eight soils and this loamy sand soil also had the smallest E2 sorption. Current modeling approaches do not take into consideration the effects of temperature fluctuations in the field because the input parameters used to describe degradation are derived from laboratory incubations at a constant temperature. Across the eight soils, E2-½ was on average 1.7 times larger and E2-TOT48 was on average 0.8 times smaller under field temperatures than under a constant 20°C. Hence, we conclude that incubations at 20°C give a reasonable representation of E2 mineralization occurring under field conditions to be expected in a typical Prairie summer season.     

Modeling adsorption kinetics of trichloroethylene onto biochars derived from soybean stover and peanut shell wastes

Trichloroethylene (TCE) is one of the most hazardous organic pollutants in groundwater. Biochar produced from agricultural waste materials could serve as a novel carbonaceous adsorbent for removing organic contaminants from aqueous media. Biochars derived from pyrolysis of soybean stover at 300 °C and 700 °C (S-300 and S-700, respectively), and peanut shells at 300 °C and 700 °C (P-300 and P-700, respectively) were utilized as carbonaceous adsorbents to study batch aqueous TCE remediation kinetics. Different rate-based and diffusion-based kinetic models were adopted to understand the TCE adsorption mechanism on biochars. With an equilibrium time of 8–10 h, up to 69 % TCE was removed from water. Biochars produced at 700 °C were more effective than those produced at 300 °C. The P-700 and S-700 had lower molar H/C and O/C versus P-300 and S-300 resulting in high aromaticity and low polarity accompanying with high surface area and high adsorption capacity. The pseudo-second order and intraparticle diffusion models were well fitted to the kinetic data, thereby, indicating that chemisorption and pore diffusion were the dominating mechanisms of TCE adsorption onto biochars.     

Transformation of diesel engine exhaust in an environmental chamber

Overnight aging experiments with diesel engine exhaust from a diesel power aggregate, with no or 9 kW load, and from a diesel-fueled vehicle were conducted in an environmental chamber. During a 24 h aging period the volatilities of monodisperse particles at 140, 250 and 360 °C heater temperatures were analyzed with volatility tandem differential mobility analysis (VTDMA). The particulate organic to total carbon ratio and organic carbon subfractions at 120, 250, 450 and 550 °C were analyzed with thermal-optical carbon analysis for samples from fresh, 8 or 18 h aged and 24 h aged aerosol. During the experiment also the particle size distribution, ozone and nitrogen oxide concentration, and temperature, relative humidity and total solar and total ultraviolet radiation in the chamber were monitored.After injection, the geometric mean diameter and number concentration of the particles in the chamber were 66–85 nm and 0.9–4.6×10⁵ cm⁻³, respectively. The particles were seen to grow fast, at a growth rate of 18–47 nm h⁻¹ during the first hour. The fresh particles from the diesel power aggregate contained 37–45% of apparent volume semi-volatile compounds with no load and 10–24% with 9 kW load. The semi-volatile apparent volume fraction at 360 °C for 50 nm particles produced by the diesel power aggregate was 57%. After 24 h of aging, the semi-volatile apparent volume fraction at 360 °C for 100 nm particles was 99%. This suggests that the particles in the 24 h aged aerosol at this size class are no more primary particles but particles that are formed in the chamber through nucleation and subsequent growth.     

The IMPROVE_A Temperature Protocol for Thermal/Optical Carbon Analysis: Maintaining Consistency with a Long-Term Database

Abstract

Thermally derived carbon fractions including organic carbon (OC) and elemental carbon (EC) have been reported for the U.S. Interagency Monitoring of PROtected Visual Environments (IMPROVE) network since 1987 and have been found useful in source apportionment studies and to evaluate quartz-fiber filter adsorption of organic vapors. The IMPROVE_A temperature protocol defines temperature plateaus for thermally derived carbon fractions of 140 °C for OC1, 280 °C for OC2, 480 °C for OC3, and 580 °C for OC4 in a helium (He) carrier gas and 580 °C for EC1, 740 °C for EC2, and 840 °C for EC3 in a 98% He/2% oxygen (O₂) carrier gas. These temperatures differ from those used previously because new hardware used for the IMPROVE thermal/optical reflectance (IMPROVE_TOR) protocol better represents the sample temperature than did the old hardware. A newly developed temperature calibration method demonstrates that these temperatures better represent sample temperatures in the older units used to quantify IMPROVE carbon fractions from 1987 through 2004. Only the thermal fractions are affected by changes in temperature. The OC and EC by TOR are insensitive to the change in temperature protocol, and therefore the long-term consistency of the IMPROVE database is conserved. A method to detect small quantities of O₂ in the pure He carrier gas shows that O₂ levels above 100 ppmv also affect the comparability of thermal carbon fractions but have little effect on the IMPROVE_TOR split between OC and EC.     

Preparation and characterisation of activated carbon from waste tea by physical activation using steam

ABSTRACT

In this study, the feasibility of preparing activated carbon from waste tea by physical activation using steam was investigated. The effects of activation temperature on yield and pore properties of the prepared activated carbon were studied. The yield decreased with increased activation temperature owing to the decomposition of cellulose and hemicellulose. The specific surface area and pore volume of the activated carbon were estimated using the Brunauer–Emmett–Teller method, Langmuir equation, and t-plot method. The specific surface area and micropore volume increased with increases in activation temperature, as additional volatile materials were released. The specific surface area significantly decreased at first but slightly increased with increasing activation time. The maximum specific surface area reached 995 m²/g at an activation temperature of 800 °C with a water flow rate of 0.075 g/min and a constant hold time of 0.5 hr. According to the nitrogen adsorption isotherms, micropores mainly developed when the activation temperature was below 800 °C, and both micropores and mesopores developed when it was above 800 °C. The results showed that activation temperature significantly affected micropore and mesopore volumes, as well as the specific surface area of the activated carbon. Overall, waste tea was found to be an attractive raw material for producing low-cost activated carbon.

Implications: Every year, a large amount of waste tea is generated after extraction. The high carbon content of waste tea showed that it can be used as raw material to produce activated carbon. This study investigated the feasibility of preparing activated carbon from waste tea by physical activation using steam. Temperature and time were found to have clear effects on pore properties. Our proposed method and raw material are more environmentally friendly and involve low cost. Furthermore, this offers a potential solution to the problems of waste tea disposal and low-cost activated carbon production.     

Predicting organic contaminant concentrations in sediment porewater using solid-phase microextraction

Because of its cost and time saving features, solid-phase microextraction (SPME) is a leading candidate as a biomimic technique in assessing the bioavailable fraction of hydrophobic organic contaminants (HOCs) in sediment porewater. However, no predictive modeling framework in which to systematically address the effect of key parameters on SPME performance for this application exists. In this study, we derived two governing equations to predict (1) the minimum sediment volume (V(s)min) required to achieve non-depletive conditions, and (2) dissolved phase HOC porewater concentrations (C(pw)) as functions of HOC- and sediment specific characteristics in a conceptual three compartment system. The resulting model predicted that V(s)min was independent of HOC concentrations both in sediment and porewater, but did vary with hydrophobicity (characterized by logK(ow)), the fraction of sediment porewater (f(pw)), and the volume (V(f)) of the SPME sorbent phase. Moreover, the effects of these parameters were minimized (i.e., V(s)min reached plateaus) as logK(ow) approached 4-5. Model predictions of C(pw), a surrogate for SPME-based detection limits in porewater, decreased with increasing sediment volume (V(s)) at low V(s) values, but rapidly leveled off as V(s) increased. A third result suggested that the sediment HOC concentration required for SPME is completely independent of K(ow). These results suggest that relatively small sediment volumes participate in exchange equilibria among sediment, porewater and the SPME fiber, and that large sediment HOC reservoirs are not needed to improve the detection sensitivity of SPME-based porewater samplers. The ultimate utility of this modeling framework will be to assist future experimental designs and help predict in situ bioavailability of sediment-associated HOCs.     

Effects of production conditions on yield and physicochemical properties of biochars produced from rice husk and oil palm empty fruit bunches

Biochar is the bio-solid material produced by pyrolysis. The biochar properties are controlled by feedstock and pyrolysis variables. In this study, the impacts of these production variables on biochar yield and physicochemical properties including pH, cation exchange capacity (CEC), total organic carbon (TOC) content, surface area, and pore volume and size were investigated. Rice husk (RH) and oil palm empty fruit bunches (EFB) were used as biomass. The biochars were produced at temperature range of 300 to 700 °C, heating rate of 3 to 10 °C/min and retention time of 1 to 3 h. The pyrolysis conditions were optimized using response surface methodology (RSM) technique to maximize the values of the responses. Analysis of variance (ANOVA) of the results demonstrated that the data fitted well to the linear and quadratic equations. Temperature was found to be the most effective parameter on the responses followed by retention time and heating rate, sequentially. CEC, TOC, surface area, and pore characteristics were evaluated as biochar properties determining their sorption potential. The optimum conditions for the maximum values of the properties were temperatures of 700 and 493.44 °C and time of 3 and 1 h for RH and EFB biochars, respectively. Heating rate at 3 °C/min was found to be the best rate for both biochars. The structure of EFB biomass was more sensitive to heating than rice husk. The biomass type and the production variables were demonstrated as the direct effective factors on biochar yield and physicochemical properties.     

Fate of methidathion residues in biological waste during anaerobic digestion

The aim of this study was to examine the fate of the organothiophosphorus pesticide methidathion during anaerobic digestion of biological waste. Three reactor experiments were conducted under various conditions of temperature, pH and retention time. The influence of pH and temperature as well as the partitioning between solid and aqueous phase were studied in batch experiments. The mesophilic (25, 35 degrees C) reactor experiments showed a decline to about 10% of the maximum methidathion concentration within 30-80 d. In the thermophilic (55 degrees C) reactor experiment, methidathion disappeared within 20 d. The batch experiments showed an abiotic hydrolysis of methidathion over the experiment period of 4 d, accelerated by alkaline conditions (pH 10.5 and 12.8) and high temperatures (55 degrees C). The hydrolysis was also noticeable at a neutral pH, while methidathion was most stable at weakly acid pH values. Methidathion bonded strongly to the biological waste, and the amount released into the water phase was below the maximum aqueous solubility. About 10% of methidathion remained non-extractable. High concentrations of dissolved organic carbon and yeast extract as a model substance for disintegrated cells further reduced the content of methidathion in the water phase, possibly caused by co-sorption to the solid organic matter.     

A New Audit Technique for EPA Method 25

A simple, inexpensive, and accurate technique for evaluating or auditing the sampling, recovery, and analytical phases of EPA Source Reference Method 25 has been developed. The technique involves spiking a U-shaped stainless steel cartridge containing Tenax® with known quantities of selected organic compounds and thermally desorbing them at temperatures from 160°C to 180°C to generate organic vapors quantitatively. The major advantages of this technique are that no other measurement methods can be used to determine the generated organic concentrations in lieu of Method 25; and that the cartridge can easily be taken to the field for evaluation. The organic compounds generated in test runs are collected and analyzed using the Method 25 procedure. The generation of organics is quantitative and recoveries were found to be 100 ± 10%. The time required for desorption of the majority of organics is generally less than forty-five minutes at a flow rate of 100 mL/min; however, based on laboratory experience the recommended sampling time is sixty minutes. These spiked cartridges are stable at room temperature over a two-month period. Results of interlaboratory studies showed close agreement with the expected concentrations based on calculations from the mass loadings and sample volumes.     

Development of a simple, accurate SPME-based method for assay of VOCs in column breakthrough experiments

Solid-phase microextraction (SPME) with gas chromatography is to be used for assay of effluent liquid samples from soil column experiments associated with VOC fate/transport studies. One goal of the fate/transport studies is to develop accurate, highly reproducible column breakthrough curves for 1,2-cis-dichloroethylene (cis-DCE) and trichloroethylene (TCE) to better understand interactions with selected natural solid phases. For SPME, the influences of the sample equilibration time, extraction temperature and the ratio of volume of sample bottle to that of the liquid sample (V(T)/V(w)) are the critical factors that could influence accuracy and precision of the measured results. Equilibrium between the gas phase and liquid phase was attained after 200 min of equilibration time. The temperature must be carefully controlled due to variation of both the Henry's constant (K(h)) and the fibre/gas phase distribution coefficient (K(fg)). K(h) decreases with decreasing temperature while K(fg) increases. Low V(T)/V(w) yields better sensitivity but results in analyte losses and negative bias of the resultant assay. High V(T)/V(w) ratio yields reduced sensitivity but analyte losses were found to be minimal, leading to better accuracy and reproducibility. A fast SPME method was achieved, 5 min for SPME extraction and 3.10 min for GC analysis. A linear calibration function in the gas phase was developed to analyse the breakthrough curve data, linear between a range of 0.9-236 microgl(-1), and a detection limit lower than 5 microgl(-1).     

Degradation of 1,4-dioxane in water with heat- and Fe2+-activated persulfate oxidation

This research investigated the 1,4-dioxane (1,4-D) degradation efficiency and rate during persulfate oxidation at different temperatures, with and without Fe²⁺ addition, also considering the effect of pH and persulfate concentration on the oxidation of 1,4-D. Degradation pathways for 1,4-D have also been proposed based on the decomposition intermediates and by-products. The results indicate that 1,4-D was completely degraded with heat-activated persulfate oxidation within 3–80 h. The kinetics of the 1,4-D degradation process fitted well to a pseudo-first-order reaction model. Temperature was identified as the most important factor influencing the 1,4-D degradation rate during the oxidation process. As the temperature increased from 40 to 60 °C, the degradation rate improved significantly. At 40 °C, the addition of Fe²⁺ also increased the 1,4-D degradation rate. Interestingly, at 50 and 60 °C, the 1,4-D degradation rate decreased slightly with the addition of Fe²⁺. This reduced degradation rate may be attributed to the rapid conversion of Fe²⁺ to Fe³⁺ and the production of an Fe(OH)₃ precipitate which limited the ultimate oxidizing capability of persulfate with Fe²⁺ under higher temperatures. Higher persulfate concentrations led to higher 1,4-D degradation rates, but pH adjustment had no significant effect on the 1,4-D degradation rate. The identification of intermediates and by-products in the aqueous and gas phases showed that acetaldehyde, acetic acid, glycolaldehyde, glycolic acid, carbon dioxide, and hydrogen ion were generated during the persulfate oxidation process. A carbon balance analysis showed that 96 and 93 % of the carbon from the 1,4-D degradation were recovered as by-products with and without Fe²⁺ addition, respectively. Overall, persulfate oxidation of 1,4-D is promising as an economical and highly efficient technology for treatment of 1,4-D-contaminated water.     

Catalytic hydrothermal treatment of pulping effluent using a mixture of Cu and Mn metals supported on activated carbon as catalyst

The present study was performed to investigate the performance of activated carbon-supported copper and manganese base catalyst for catalytic wet oxidation (CWO) of pulping effluent. CWO reaction was performed in a high pressure reactor (capacity?=?0.7 l) at temperatures ranging from 120 to 190 °C and oxygen partial pressures of 0.5 to 0.9 MPa with the catalyst concentration of 3 g/l for 3 h duration. With Cu/Mn/AC catalyst at 190 °C temperature and 0.9 MPa oxygen partial pressures, the maximum chemical oxygen demand (COD), total organic carbon (TOC), lignin, and color removals of 73, 71, 86, and 85 %, respectively, were achieved compared to only 52, 51, 53, and 54 % removals during the non-catalytic process. Biodegradability (in terms of 5-day biochemical oxygen demand (BOD₅) to COD ratio) of the pulping effluent was improved to 0.38 from an initial value of 0.16 after the catalytic reaction. The adsorbed carbonaceous fraction on the used catalyst was also determined which contributed meager TOC reduction of 3–4 %. The leaching test showed dissolution of the metals (i.e., Cu and Mn) from the catalysts in the wastewater during CWO reaction at 190 °C temperature and 0.9 MPa oxygen partial pressures. In the future, the investigations should focus on the catalyst reusability.     

Adsorption of organic vapors on polar surfaces- Recent advances

This paper summarizes recent research on the adsorption of organic vapors on surfaces. Since the low gas phase concentration range is typical for environmental situations, this review is restricted to these adsorption coefficients. Two environmental parameters have a strong influence on the adsorption of organic vapors on polar surfaces:temperature andrelative humidity (which is the most suitable parameter for describing the influence of ambient moisture). An exponential relationship was found for the adsorption coefficientversus relative humidity and the reciprocal temperature, respectively. Comparing the heats of adsorption, two different groups of substances emerged: polar chemicals exhibited heats of sorption which were higher than their corresponding heats of condensation due to their ability to form hydrogen bonds, while for the nonpolar compounds the opposite was true. Sorption takes place on the surface of an adsorbed water film when the relative humidity exceeds the value which is necessary to form a monomolecular layer of water on the surface of the adsorbent (≥ 30 % relative humidity). Therefore, at temperature below 0 °C, a change in the adsorption behavior might be expected due to a change of properties of the adsorbed water film. However, no alterations were observed at temperatures from -12 °C to + 4 °C (adsorption on quartz sand). The results were comparable to those at much higher temperatures (50 – 80 °C). A statistical approach for the prediction of the adsorption coefficients from physico-chemical parameters of the substances (vapor pressure, polarizability, and electron-donating capability) was developed and good agreement was found with experimental results and independent data from the literature. Finally, two special cases, the adsorption on bulk water and ice, are discussed.     

Temperature influence on biological phosphorus removal induced by aerobic/extended-idle regime

Previous researches have demonstrated that biological phosphorus removal (BPR) from wastewater could be driven by the aerobic/extended-idle (A/EI) regime. This study further investigated temperature effects on phosphorus removal performance in six A/EI sequencing batch reactors (SBRs) operated at temperatures ranging from 5 to 30 °C. The results showed that phosphorus removal efficiency increased with temperature increasing from 5 to 20 °C but slightly decreased when temperature continually increased to 30 °C. The highest phosphorus removal rate of 97.1 % was obtained at 20 °C. The biomass cultured at 20 °C contained more polyphosphate accumulating organisms (PAO) and less glycogen accumulating organisms (GAO) than that cultured at any other temperatures investigated. The mechanism studies revealed that temperature affected the transformations of glycogen and polyhydroxyalkanoates, and the activities of exopolyphosphatase and polyphosphate kinase activities. In addition, phosphorus removal performances of the A/EI and traditional anaerobic/oxic (A/O) SBRs were compared at 5 and 20 °C, respectively. The results showed the A/EI regime drove better phosphorus removal than the A/O regime at both 5 and 20 °C, and more PAO and less GAO abundances in the biomass might be the principal reason for the higher BPR in the A/EI SBRs as compared with the A/O SBRs.     

Laboratory Evaluations of the Thermal Degradation Properties of Toxic Organic Materials in Sewage Sludge

Laboratory thermal decomposition studies were performed to evaluate potential emissions from sewage sludge incinerators. Precisely controlled thermal decomposition experiments were conducted on sludge spiked with mixtures of hazardous organic compounds, on mixtures of pure compounds without sludge, and on unspiked sludge. Experiments were conducted in nitrogen and air atmospheres with gas phase reaction times of 2.0 seconds over the temperature range 300°C-1000°C.

It was found that sludge inhibited the decomposition of moderately stable spiked contaminants but accelerated the decomposition of the most stable components. This effect was attributed to radical scavengers produced by the sludge matrix at lower temperatures which then decomposed at higher temperatures. A multiple hearth simulation study suggested that most of the organic material present In the sludge matrix is vaporized within the upper hearths that are held at lower temperatures and may consequently escape from such incinerators undestroyed. A number of stable byproducts resulted from the sludge decomposition that may be of environmental concern.     

Analysis of Organophosphorus Pesticides in Whole Milk by Solid Phase Microextraction Gas Chromatography Method

Solid phase microextraction (SPME) was used for the extraction of residual coumaphos and dichlorvos in whole milk. The residues were analyzed by capillary gas chromatography equipped with nitrogen phosphorus detector (GC-NPD). A manual SPME holder with a 100-μm polyacrylate fiber was used. The optimized conditions for extraction by SPME method were: sample agitation, absorption temperature of 30°C, absorption time of 40 min, desorption time of 10 min, and sample volume was 16.0 mL in the vial. Under these conditions, the calibration graphs were linear in the range of 0.17 μgL^?1 to 1.75 μgL^?1 for coumaphos and 0.69 μgL^?1 to 6.90 μgL^?1 for dichlorvos. Precision was good with RSD values of 13% for coumaphos and 14% for dichlorvos. The detection limits (LOD) were 0.060 μgL^?1 for dichlorvos and 0.052 for coumaphos. The quantification limits (LOQ) were 0.086 μgL^?1 for dichlorvos and 0.066 μgL^?1 for coumaphos. The results obtained in this study suggest that SPME is a suitable technique for residual pesticide analysis of milk. The data demonstrate that particular OP pesticides used in dairy farming in the region of Minas Gerais were found to contaminate cow whole milk, and the residues are not removed by treating the milk by boiling.     

Benzyl-penicillin (Penicillin G) transformation in aqueous solution at low temperature under controlled laboratory conditions

Antibiotics are released into the environment in a variety of ways: via wastewater effluent as a result of incomplete metabolism in the body after use in human therapy, as runoff after use in agriculture, through improper disposal by private households or hospitals or through insufficient removal by water treatment plants. Unlike in most European countries, in Arctic regions effluents are not suitably treated prior to their release into the aquatic environment. Also, many of the scattered human settlements in remote regions of the Arctic do not possess sewage treatment facilities and pharmaceutical residues therefore enter the aqueous environment untreated.Only limited data are available on the biodegradation of antibiotics under Arctic conditions. However, such information is needed to estimate the potential harm of antibiotics for the environment. Pen-G is used in this study since it is a widely prescribed antibiotic compound whose environmental properties have not yet been investigated in detail. Thus, for a very first assessment, the OECD approved biodegradation Zahn–Wellens test (ZWT, OECD 302 B) was used to study biodegradation and non-biotic elimination of the antibiotic Benzyl-penicillin (Pen-G) at different temperatures (5 °C, 12.5 °C and 20 °C). The testing period was extended from the OECD standard of 28–42 d. In addition to dissolved organic carbon (DOC), Pen-G levels and major transformation products were recorded continuously by LC-ion-trap-MS/MS. DOC monitoring revealed considerable temperature dependence for the degradation process of Pen-G. DOC loss was slowest at 5 °C and considerably faster at 12.5 °C and 20 °C. In the initial step of degradation it was found that Pen-G was hydrolyzed. This hydrolyzed Pen-G was subsequently further degraded by decarboxylation, the result of which was 2-(5,5-dimethyl-1,3-thiazolidin-2-yl)-2-(2-phenylacetamido)acetic acid. Furthermore, direct elimination of 2-phenyl-acetaldehyde from the hydrolyzed and decarboxylated Pen-G also led to the formation of 2-[amino(carboxy)methyl]-5,5-dimethyl-1,3-thiazolidone-4-carboxylic acid. Since biodegradation slows down considerably at a low temperature, the resulting transformation products had considerably longer residence times at 5 °C compared to higher temperature conditions within the 42-d experiment. The results presented here clearly demonstrate that a risk assessment for pharmaceuticals present in low ambient temperature environments (i.e. the Arctic) cannot be based on test results obtained under standard laboratory conditions (i.e. 20 °C ambient temperatures).