Formation of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) from a refinery process for zinc oxide used in feed additives: a source of dioxin contamination in Chilean pork

The Republic of Korea found dioxin at concentrations exceeding the Korean maximum residue limit (MRL) in pork (2 pg TEQ g⁻¹ fat) imported from Chile in June 2008. Korea and Chile collaborated and investigated to find out the sources of contamination. An isotope dilution method and high resolution gas chromatography/mass spectrometry (HR-GC/MS) were used for the analysis of PCDD/Fs. PCDD/Fs were found from 2.17 to 36.7 pg TEQ g⁻¹ fat from Chilean pork. 2,3,4,7,8-PeCDF, 1,2,3,4,7,8-HxCDF, 1,2,3,6,7,8-HxCDF, and 2,3,4,6,7,8-HxCDF were found as the major congeners in pork samples. 2,3,4,7,8-PeCDF showed the highest concentration and contributed about 30% among the congeners in most of the samples. 2,3,7,8-TCDD, 1,2,3,7,8,9-HxCDD, OCDD, 2,3,7,8-TCDF, 1,2,3,7,8-PeCDF, 1,2,3,7,8,9-HxCDF, and OCDF were not detected or exist at background levels in the less contaminated samples. Remarkably high concentrations of PCDD/Fs were found in samples of zinc oxide (17 147 pg TEQ g⁻¹), zinc oxide based premix (6673 pg TEQ g⁻¹), and the residue crust (800 pg TEQ g⁻¹) in a mixing chamber in the feed mill. From the results of various investigations, this case concluded that zinc oxide in the feed was the major source of the dioxin contamination in pork. The dioxins were formed from a metal refinery process to collect zinc oxide.     

Adsorption characteristics of Cu2+ and Zn2+ from aqueous solution using carbonized food waste

The aim of the present study was to analytically provide adsorption characteristics of Cu²⁺ and Zn²⁺ using carbonized food waste (CFW); more specifically, batch tests were conducted using various concentrations of metal ions, contact times, and initial pH levels in an attempt to understand the adsorption removal of heavy metal ions in aqueous solution at concentrations ranging between 50 and 800 mg/l. The results confirmed that the adsorption equilibrium was established within a maximum of 80 min, and the maximum concentrations for adsorption of Cu²⁺ and Zn²⁺ were 28.3 and 23.5 mg/g, respectively. These adsorption levels indicate that CFW has better performance than many other adsorbents. In experiments using different pH conditions, the applicability to acid wastewater was found to be high, and an excellent adsorption removal ratio of 75%–90% was observed under acid conditions at pH 2–4. Furthermore, as the adsorption time increased, the calcium component in the CFW began to leach into the aqueous solution and raise the pH, accordingly causing the removal of heavy metal ions partially as a result of precipitation. When our results were analyzed using the Langmuir model and the Freundlich model for isothermal adsorptivity, the activity of CFW in this study was shown to be more consistent with the former; the adsorption speed of Cu²⁺ and Zn²⁺ according to a pseudosecond-order reaction model was found to be very fast for an initial concentration of not more than 100 mg/l. In a test in which an attempt was made to compare adsorption capacity values obtained from the experiments in this study with the aforementioned three models, the pseudosecond-order reaction model was found to provide results closest to the actual values.     

Personal exposure of graduate students attending the college of natural sciences or social sciences to volatile organic compounds on campus

The present study measured the levels of 24 selected volatile organic compounds (VOCs) in the personal air samples obtained from graduate students attending the college of natural sciences (GSNSs) or social science (GSSSs) during their daily activities on campus along with associated indoor and outdoor air samples. In addition, the sources of their personal exposure were characterized using multivariate statistical models. In the personal samples of GSNSs and GSSSs, 16 and 15 different VOCs were always detected, respectively. The personal exposure of five chlorinated hydrocarbons and six aromatics was significantly higher for GSNSs than for GSSSs. Consistently, the indoor levels of these compounds were higher for GSNSs (in research and laboratory rooms) than for GSSSs (in research rooms). However, the personal exposure of two aromatic VOCs (1,2,4- and 1,3,5-trimethylbenzene) was higher for GSSSs. Moreover, the personal exposure of the five chlorinated and six aromatic compounds was significantly correlated with VOC concentrations both in the research and laboratory rooms of GSNSs and with those in the research rooms of GSSSs. For certain VOCs, outdoor sources were also a major contributor to the personal exposure of both GSNSs and GSSSs. The multivariate models identified five factors that accounted for 81% of the total variance and four factors that explained 76% of the total variance. It was further suggested that multiple indoor sources in research rooms such as office equipment, building finishing materials, and air fresheners were the main source for the personal exposure to VOCs for GSNSs, whereas building finishing materials were the main source for GSSSs.     

Empirical correlations to estimate agglomerate size and deposition during injection of a polyelectrolyte-modified Fe0 nanoparticle at high particle concentration in saturated sand

Controlled emplacement of polyelectrolyte-modified nanoscale zerovalent iron (NZVI) particles at high particle concentration (1-10 g/L) is needed for effective in situ subsurface remediation using NZVI. Deep bed filtration theory cannot be used to estimate the transport and deposition of concentrated polyelectrolyte-modified NZVI dispersions (>0.03 g/L) because particles agglomerate during transport which violates a fundamental assumption of the theory. Here we develop two empirical correlations for estimating the deposition and transport of concentrated polyelectrolyte-modified NZVI dispersions in saturated porous media when NZVI agglomeration in porous media is assumed to reach steady state quickly. The first correlation determines the apparent stable agglomerate size formed during NZVI transport in porous media for a fixed hydrogeochemical condition. The second correlation estimates the attachment efficiency (sticking coefficient) of the stable agglomerates. Both correlations are described using dimensionless numbers derived from parameters affecting deposition and agglomeration in porous media. The exponents for the dimensionless numbers are determined from statistical analysis of breakthrough data for polyelectrolyte-modified NZVI dispersions collected in laboratory scale column experiments for a range of ionic strength (1, 10, and 50mM Na(+) and 0.25, 1, and 1.25 mM Ca(2+)), approach velocity (0.8 to 55 × 10(-4)m/s), average collector sizes (d(50)=99 μm, 300 μm, and 880 μm), and polyelectrolyte surface modifier properties. Attachment efficiency depended on approach velocity and was inversely related to collector size, which is contrary to that predicted from classic filtration models. High ionic strength, the presence of divalent cations, lower extended adsorbed polyelectrolyte layer thickness, decreased approach velocity, and a larger collector size promoted NZVI agglomeration and deposition and thus limited its mobility in porous media. These effects are captured quantitatively in the two correlations developed. The application and limitations of using the correlations for preliminary design of in situ NZVI emplacement strategies is discussed.     

The rhizosphere and PAH amendment mediate impacts on functional and structural bacterial diversity in sandy peat soil

To reveal the degradation capacity of bacteria in PAH polluted soil and rhizosphere we combined bacterial extradiol ring-cleavage dioxygenase and 16S rRNA analysis in Betula pubescens rhizoremediation. Characterisation of the functional bacterial community by RFLP revealed novel environmental dioxygenases, and their putative hosts were studied by 16S rRNA amplification. Plant rhizosphere and PAH amendment effects were detected by the RFLP/T-RFLP analysis. Functional species richness increased in the birch rhizosphere and PAH amendment impacted the compositional diversity of the dioxygenases and the structural 16S rRNA community. A shift from an Acidobacteria and Verrucomicrobia dominated to an Alpha- and Betaproteobacteria dominated community structure was detected in polluted soil. Clone sequence analysis indicated catabolic significance of Burkholderia in PAH polluted soil. These results advance our understanding of rhizoremediation and unveil the extent of uncharacterized functional bacteria to benefit bioremediation by facilitating the development of the molecular tool box to monitor bacterial populations in biodegradation.     

Leaf age affects the responses of foliar injury and gas exchange to tropospheric ozone in Prunus serotina seedlings

We investigated the effect of leaf age on the response of net photosynthesis (A), stomatal conductance (g_wv), foliar injury, and leaf nitrogen concentration (N_L) to tropospheric ozone (O₃) on Prunus serotina seedlings grown in open-plots (AA) and open-top chambers, supplied with either carbon-filtered or non-filtered air. We found significant variation in A, g_wv, foliar injury, and N_L (P < 0.05) among O₃ treatments. Seedlings in AA showed the highest A and g_wv due to relatively low vapor pressure deficit (VPD). Older leaves showed significantly lower A, g_wv, N_L, and higher foliar injury (P < 0.001) than younger leaves. Leaf age affected the response of A, g_wv, and foliar injury to O₃. Both VPD and N_L had a strong influence on leaf gas exchange. Foliar O₃-induced injury appeared when cumulative O₃ uptake reached 8-12 mmol m⁻², depending on soil water availability. The mechanistic assessment of O₃-induced injury is a valuable approach for a biologically relevant O₃ risk assessment for forest trees.     

Improving ozone modeling in complex terrain at a fine grid resolution: Part I – examination of analysis nudging and all PBL schemes associated with LSMs in meteorological model

Meteorological variables such as temperature, wind speed, wind directions, and Planetary Boundary Layer (PBL) heights have critical implications for air quality simulations. Sensitivity simulations with five different PBL schemes associated with three different Land Surface Models (LSMs) were conducted to examine the impact of meteorological variables on the predicted ozone concentrations using the Community Multiscale Air Quality (CMAQ) version 4.5 with local perspective. Additionally, the nudging analysis for winds was adopted with three different coefficients to improve the wind fields in the complex terrain at 4-km grid resolution. The simulations focus on complex terrain having valley and mountain areas at 4-km grid resolution. The ETA M–Y (Mellor–Yamada) and G–S (Gayno–Seaman) PBL schemes are identified as favorite options and promote O₃ formation causing the higher temperature, slower winds, and lower mixing height among sensitivity simulations in the area of study. It is found that PX (Pleim–Xiu) simulation does not always give optimal meteorological model performance. We also note that the PBL scheme plays a more important role in predicting daily maximum 8-h O₃ than land surface models. The results of nudging analysis for winds with three different increased coefficients' values (2.5, 4.5, and 6.0 × 10^?4 s^?1) over seven sensitivity simulations show that the meteorological model performance was enhanced due to improved wind fields, indicating the FDDA nudging analysis can improve model performance considerably at 4-km grid resolution. Specifically, the sensitivity simulations with the coefficient value (6.0 × 10^?4) yielded more substantial improvements than with the other values (2.5 and 4.5 × 10^?4). Hence, choosing the nudging coefficient of 6.0 × 10^?4 s^?1 for winds in MM5 may be the best choice to improve wind fields as an input, as well as, better model performance of CMAQ in the complex terrain area. As a result, a finer grid resolution is necessary to evaluate and access of CMAQ results for giving a detailed representation of meteorological and chemical processes in the regulatory modeling. A recommendation of optimal scheme options for simulating meteorological variables in the complex terrain area is made.     

An examination of antecedents to coal miners' hearing protection behaviors: a test of the theory of planned behavior

PROBLEM: The National Institute for Occupational Safety and Health's [NIOSH] National Occupational Research Agenda (DHHS Publication No. 96-115) reports that approximately 50% of miners will experience hearing loss by age 50, compared to only 9% of the general population. The present investigation examines three antecedents believed to be associated with miner's use of hearing protection. METHOD: A posttest-delayed-posttest-control group field research design was employed to assess antecedents toward wearing hearing protection. RESULTS: Following the initial posttest, miners' attitudes and subjective norms were antecedents to intentions to wear hearing protection devices. Also, intentions toward wearing hearing protection predicted hearing protection behaviors. Approximately six weeks later, miners' attitudes and perceived behavioral control were each significant predictors of intentions to wear hearing protection and again, intentions were positively associated with hearing protection behaviors. IMPACT ON INDUSTRY: Our results indicate that appeals to normative influences may be the most effective antecedent to employ when persuading coal miners to wear hearing protection. However, messages designed to impact attitudes and perceived behavioral control were also effective.     

Rhamnolipid morphology and phenanthrene solubility at different pH values

The effect of pH and rhamnolipids on the solubility of phenanthrene was investigated in a sand-water system. Batch phenanthrene solubilization experiments in this system showed that the highest phenanthrene solubility occurred at pH 5 in the presence of 240 and 150 mg L(-1) rhamnolipids. As the pH was increased from 5 to 7, the apparent solubility of phenanthrene decreased and then stabilized from pH 7 to 8. At pH 4, a dramatic decrease in phenanthrene solubility was observed. This result is in contrast to previous findings obtained in an aqueous system without soil particles. To investigate the reason for this decrease, the critical micelle concentrations (CMCs) were measured in the presence or absence of sand particles, and the maximum amount of sorbed biosurfactant at each pH was calculated based on the differences of the two CMC values. More rhamnolipid molecules were lost by the sorption into sand particles at pH 4 than at other pH values; this explains the dramatic decrease of solubility at pH 4 in the sand-water system. To confirm the explanation for the different solubilizing capacity that results from the structural change of biosurfactant aggregate, cryo-transmission electron microscopy was used. Micrographs showed that the rhamnolipid morphology changed from large lamellar sheets, to vesicle, and then to micelle as the pH increased. The large and multilamellar vesicles at pH 5 were considered to be the most effective structure for the solubilization of phenanthrene.