A new method of predicting of gas chromatographic retention indices for polychlorinated dibenzofurans (PCDFs)

A new method has been developed to describe the quantitative relationship between molecular structures of PCDFs and their gas chromatographic retention indices on a 30-m fused silica column coated with DB-5 stationary phase. The regression equation is derived with a multiple correlation coefficient greater than 0.9995. The highest residual is 20 index units. The standard deviation is less than 7 index units. Using this regression equation, the retention indices of PCDFs for which data is not available have also been predicted.     

Quantitative structure-activity relationships for polycyclic aromatic hydrocarbons: Correlation between molecular connectivity,physico-chemical properties,bioconcentration and toxicity in Daphnia pulex

High correlation coefficients (r = 0.9444 – 0.9996) were calculated for the linear one-parameter correlation between molecular weight, molecular connectivity indices, HPLC and TLC retention indices, partition coefficients between n-octanol or sediment and water, and bioconcentration factors or lethal concentrations in Daphnia Pulex of unsubstituted polycyclic aromatic hydrocarbons.     

Estimation of selected physicochemical properties for methylated naphthalene compounds

Liquid aqueous solubility (S(w,L)), octanol/water partition coefficients (K(ow)), liquid vapor pressure (P(v,L)), and Henry's law constants (H(c)) were estimated for 20 methylated naphthalenes ranging from monomethyl to tetramethylnaphthalenes. Chromatographic methods were used for the estimation. Chromatographic retention measurements were conducted for 11 reference compounds and regressions were fit between the retention indices and the physicochemical properties. HPLC octadecylsilyl column with acetonitrile/water eluent was used for the estimation of S(w,L) and K(ow). Two GC columns, HP5-MS and a more hydrophobic HP-1, were tested for the estimation of P(v,L). Measured retention indices for the methylated naphthalenes were entered to the regression equations to calculate the physicochemical properties for these compounds. Literature values, where available, were used to validate the calculated values. The method accurately estimated the physicochemical properties. Estimated S(w,L) and P(v,L) decreased with the number of methyl groups. K(ow) increased with the number of methyl groups. There was no obvious relation between H(c) and the number of methyl groups. Log S(w,L) ranged from 0.885 for 1,2,5,6-tetramethylnaphthalene to 2.269 for 1-methylnaphthalene (mmol/m(3)). Log K(ow) varied from 3.89 for 1-methylnaphthalene to 4.95 for 1,2,5,6-tetramethylnaphthalene. Log P(v,L) ranged from -0.983 for 1,2,5,6-tetramethylnaphthalene to 0.789 for 2-methylnaphthalene (Pa). Log H(c) varied from 1.03 for 1,4,5-trimethylnaphthalene to 1.73 for 2,6-dimethylnaphthalene (Pa m(3)/mol). There were no apparent effects of GC column hydrophobicity on the accuracy of the results. Estimation of S(w,L) and K(ow) based on GC retention indices was not as accurate as with HPLC. Comparison of the estimated values with values predicted by EPIWIN indicated that EPIWIN is useful in giving order-of-magnitude prediction of physicochemical properties.     

Relationships of ozone exposure to pine injury in the Sierra Nevada and San Bernardino Mountains of California, USA

Hourly ambient ozone exposure data and crown injury measurements were gathered in the Sierra Nevada and San Bernardino Mountains of California to develop relationships between the Ozone Injury Index (OII), the Forest Pest Management Index (FPM), chlorotic mottle, fascicle retention (OII index components) and cumulative ambient ozone indices for Pinus ponderosa Dougl. ex Laws and Pinus jeffreyi Grev. and Balf. Eleven sites located in the mixed conifer forest near ambient ozone monitoring sites were evaluated annually for 4 years. Four other sites in the San Bernardino Mountains were evaluated for 1 year. Analyses showed OII to be functionally equivalent (r2 = 0.96) to the FPM, and to depend only on fascicle retention and chlorotic mottle (R2 = 0.95) of the fourth whorl (or if four whorls are not present at the site, then the last whorl present for the majority of trees). Significant associations were found between OII and 4-year 24-h. summer SUM0, SUM06, W126 and HRS80 ozone indices. Three sites had higher levels of cumulative chlorotic mottle for individual whorls and larger numbers of trees with visible crown injury than other sites with similar cumulative ambient ozone levels. Including an indicator variable to discriminate between these two groups of sites increased R2 and decreased root mean square (RMSE) for all indices, especially SUM0 (R2 = 0.93, RMSE reduced by 46%).     

Characterization of organic coatings on hygroscopic salt particles and their atmospheric impacts

The photooxidation of α-pinene in the presence of NO₂, with and without added NaNO₃ seed particles, has been studied in a large-diameter flow tube. Particles formed by homogeneous nucleation and by condensation on the pre-existing seeds were sampled at various stages of the reaction, dried using four diffusion dryers, size selected at different mobility diameters (d_m) using a differential mobility analyzer (DMA), and characterized with a single particle mass spectrometer (SPLAT II). It was found that homogeneously nucleated particles are spherical, have a density (ρ) of 1.25 ± 0.02 g cm^?3 (±2σ) and contain a significant amount of organic nitrates. The mass spectra of the low volatility products condensed on the NaNO₃ seed particles were found to be virtually the same as in the case of homogeneous nucleation. The data show that the presence of even a submonolayer of organics on the NaNO₃ particles causes water retention that leads to a decrease in particle density and that the amount of water retained increases with organic coating thickness. Thicker coatings appear to inhibit water evaporation from the particle seeds altogether. This suggests that in the atmosphere, where low volatility organics are plentiful, some hygroscopic salts will retain water and have different densities and refractive indices than expected in the absence of the organic coating. This water retention combined with the organic shell on the particles can potentially impact light scattering by these particles and activity as cloud condensation nuclei (CCN), as well as heterogeneous chemistry and photochemistry on the particles.     

Relative retention times of chlorinated monoterpenes

GC retention times for 67 chlorinated monoterpenes, belonging to the technical pesticide Toxaphene have been measured under the same conditions and relative retention times have been determined. They consisted of 45 chlorinated bornanes, 13 chlorinated bornenes, 8 chlorinated dihydrocamphenes and 1 chlorinated camphene. Useful correlations between structure and retention time were found. Similar changes in structure for different compounds lead to similar changes in retention times. These correlations allow to predict retention times for yet unknown Toxaphene congeners.     

Sensory and chemical characterization of VOC emissions from building products: impact of concentration and air velocity

The emissions from five commonly used building products were studied in small-scale test chambers over a period of 50 days. The odor intensity was assessed by a sensory panel and the concentrations of selected volatile organic compounds (VOCs) of concern for the indoor air quality were measured. The building products were three floor coverings: PVC, floor varnish on beechwood parquet and nylon carpet on a latex foam backing; an acrylic sealant, and a waterborne wall paint on gypsum board. The impacts of the VOC concentration in the air and the air velocity over the building products on the odor intensity and on the emission rate of VOCs were studied. The emission from each building product was studied under two or three different area-specific ventilation rates, i.e. different ratios of ventilation rate of the test chamber and building product area in the test chamber. The air velocity over the building product samples was adjusted to different levels between 0.1 and 0.3 m s^-1. The origin of the emitted VOCs was assessed in order to distinguish between primary and secondary emissions. The results show that it is reasonable after an initial period of up to 14 days to consider the emission rate of VOCs of primary origin from most building products as being independent of the concentration and of the air velocity. However, if the building product surface is sensitive to oxidative degradation, increased air velocity may result in increased secondary emissions. The odor intensity of the emissions from the building products only decayed modestly over time. Consequently, it is recommended to use building products which have a low impact on the perceived air quality from the moment they are applied. The odor indices (i.e. concentration divided by odor threshold) of primary VOCs decayed markedly faster than the corresponding odor intensities. This indicates that the secondary emissions rather than the primary emissions, are likely to affect the perceived air quality in the long run. Some of the building products continued to affect the perceived air quality despite the concentrations of the selected VOCs resulted in odor indices less than 0.1. Therefore, odor indices less than 0.1 as an accept criterion cannot guarantee that a building product has no impact on the perceived air quality.     

Peak identification for PCDD/Fs in environmental samples at different temperature programs

A method has been developed for peak recognition of 136 polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) at different temperature programs. Their retention behaviours are predicted on the basis of an identification database of retention values (A, B) of gas chromatography. By the retention times of 13C labelled 2,3,7,8-substituted PCDD/F internal standards, the retentions of all PCDDs and PCDFs can be calculated. After comparison with the retentions of practical environmental samples, the predicted values have been proved to be very accurate.     

Dissecting the ecosystem service of large-scale pollutant retention: The role of wetlands and other landscape features

Various features of a landscape contribute to the regulating ecosystem service of reducing waterborne pollutant loading to downstream environments. At local scales, wetlands have been shown to be effective in retaining pollutants. Here, we investigate the landscape-scale contribution to pollutant retention provided by multiple wetlands. We develop a general analytical model which shows that the retention contribution of wetlands and other landscape features is only significant if a large fraction of the total waterborne pollutant transport passes through them. Next, by means of a statistical analysis of official data, we quantify the nutrient retention contribution of wetlands for multiple sub-catchments in two Swedish Water Management Districts. We compare this with the retention contribution of two other landscape features: the waterborne transport distance and major lakes. The landscape-scale retention contribution of wetlands is undetectable; rather, the other two landscape features account for much of the total nutrient retention.     

Laboratory experiments on simultaneous removal of K and P from synthetic and real urine for nutrient recycle by crystallization of magnesium-potassium-phosphate-hexahydrate in a draft tube and baffle reactor

The simultaneous removal of K and P from urine for nutrient recycling by crystallization of magnesium potassium phosphate hexahydrate (MPP) in a laboratory-scale draft tube and baffle reactor (DTBR) is investigated. Results show that mixing speed and hydraulic retention time are important operating factors that influence crystallization and crystal settlement. Slurry should be discharged at a crystal retention time of 11 h to maintain fluidity in the reactor. Further applications of the DTBR using real urine (pretreated by ammonia stripping and diluted five times) showed that 76% K and 68% P were recycled to multi-nutrient products. The crystals collected were characterized and confirmed mainly as a mixture of magnesium ammonium phosphate hexahydrate, MPP, and magnesium sodium phosphate heptahydrate. Results indicate that the DTBR effectively achieved the simultaneous recycling of K and P from urine to multi-nutrient products through MPP crystallization.     

Collection of vapors of selected chlorocarbons and benzene on Tenax GC

Breakthrough and retention volume studies have been done for a series of chlorocarbon compounds on Tenax GC adsorbent with results compared to data of other workers. Initial data indicates that carrier velocity (Time to establish equilibrium) may significantly effect retention of these chemicals.     

Identification and quantification of new polybrominated dimethoxybiphenyls (PBDMBs) in marine mammals from Australia

Marine mammals from Queensland, Australia, are bioaccumulating elevated concentrations of a range of polybrominated natural products. In this study, we detected three new polybrominated dimethoxybiphenyls (PBDMBs) in the blubber of selected marine mammal samples which were identified as 2,6'-dimethoxy-3,3',5-tribromobiphenyl (2,6'-diMeO-BB 36), 2,2'-dimethoxy-3,3'-dibromobiphenyl (2,2'-diMeO-BB 36), and 6,6'-dimethoxy-3,3'-dibromobiphenyl (6,6'-diMeO-BB 11). These three PBDMBs are structurally related to the known natural product 2,2'-dimethoxy-3,3',5,5'-tetrabromobiphenyl (2,2'-diMeO-BB 80). In the first part of this study, 2,2'-diMeO-BB 80 was photochemically debrominated under UV irradiation. This resulted in seven of eight possible mono- to triBDMBs as debromination products. In the second part of this study, the structure of all PBDMBs debromination products was investigated. This was supported by synthesis of two diBDMB and one triBDMB via bromination and subsequent methylation of 2,2'-biphenyldiol. Structures of the remaining PBDMBs were tentatively assigned by considering the retention times, mass spectra and amounts formed during UV irradiation of 2,2'-diMeO-BB 80 . In the third part of this study, blubber of marine mammals from Australia was analysed for PBDMBs using gas chromatography in combination with electron ionization mass spectrometry (GC/EI-MS) in the selected ion monitoring mode. In these samples, 2,2'-diMeO-BB 80 was found at concentrations of 200-1800ngg(-1) lipid weight (lw). The latter represents the highest concentration reported for this compound in environmental samples. 6,6'-diMeO BB 11, 2,2'-diMeO BB 36, and 2,6'-diMeO BB 36 were present at approximately 7ngg(-1) lipids, or 0.43-1.5% of diMeO-BB 80. No further PBDMBs were detected in the samples. The di- and triBDMBs identified in marine mammal blubber have not been reported as natural products. They may represent either new natural products or transformation products of 2,2'-diMeO-BB 80.     

A pilot study of mercury liberation and capture from coal-fired power plant fly ash

The coal-fired electric utility generation industry has been identified as the largest anthropogenic source of mercury (Hg) emissions in the United States. One of the promising techniques for Hg removal from flue gas is activated carbon injection (ACI). The aim of this project was to liberate Hg bound to fly ash and activated carbon after ACI and provide high-quality coal combustion products for use in construction materials. Both bench- and pilot-scale tests were conducted to liberate Hg using a thermal desorption process. The results indicated that up to 90% of the Hg could be liberated from the fly ash or fly-ash-and-activated-carbon mixture using a pilot-scale apparatus (air slide) at 538 degrees C with a very short retention time (less than 1 min). Scanning electron microscope (SEM) evaluation indicated no significant change in fly ash carbon particle morphology following the thermal treatment. Fly ash particles collected in the baghouse of the pilot-scale apparatus were smaller in size than those collected at the exit of the air slide. A similar trend was observed in carbon particles separated from the fly ash using froth flotation. The results of this study suggest a means for power plants to reduce the level of Hg in coal-combustion products and potentially recycle activated carbon while maintaining the resale value of fly ash. This technology is in the process of being patented.     

An atmospheric stability index based on radon progeny measurements for the evaluation of primary urban pollution

An atmospheric stability index for the evaluation of urban primary pollution, based on the elaboration of natural radioactivity data yielded by a stability monitor, has been developed. The instrument determines the atmospheric concentration of the short-lived decay products of radon, whose emanation rate can be assumed to be constant in the time and space scale of observation. The index gives information about the dilution properties of the lower boundary layer and allows to highlight the relevant role of the dilution factor in determining primary pollution events.The atmospheric stability indices have been calculated during a 1-yr study carried out in the urban area of Rome (October 1999–September 2000). On the basis of the index, every day of the period has been classified in terms of intensity of a potential primary pollution event. The comparison between this classification and the real concentration value of primary pollutants, measured in the background urban station of Rome, yielded very good results. This shows that the index constitutes a powerful and valuable tool for describing primary pollution events in urban areas and confirms that the role played by the mixing properties of the lower boundary layer is essential in determining primary pollution in urban areas.     

中水生化处理的最佳停留时间

本文研究了洗浴废水在生物转盘中不同停留时间的处理效果。研究结果显示 :在停留时间为 0 .2 5— 1.5h内 ,洗浴废水中的CODCr、BOD5、SS和LAS的去除率随停留时间的增加其增幅较大 ,但随着停留时间的继续延长 ,去除率增加幅度逐渐变小 ,研究结果表明 ,洗浴废水生物处理的最佳停留时间为 1.5h。     

Use of coal to retard pesticide movement in soil

Abstract

Three different coals and an activated carbon were mixed with prescribed amounts of a sandy loam soil and added to soil columns to test their ability to retard pesticide movement. The pesticides chosen were prometon, prometryn, 2,4‐D, carbofuran, dinoseb, fenamiphos, and two oxidation products of fenamiphos, fenamiphos sulfoxide, and fenamiphos sulfone. These compounds were chosen to represent different chemical classes of pesticides and because they were considered to have a high potential for transport in soils. All the coals were more effective in retaining the pesticides than the soil, however, some were more effective than others. One of the coals was the most effective in retaining the majority of the pesticides with an overall retention of 94.7% in a 4:1 soil/coal ratio compared to the soil only with a retention of 48.5%. The moisture content of the coal appears to have a positive correlation with the ability of the coal to retain the pesticides under the conditions used for this experiment.