Calibration and field verification of semipermeable membrane devices for measuring polycyclic aromatic hydrocarbons in water

The use of semipermeable membrane devices (SPMDs) has become common in environmental sampling of nonpolar organic contaminants, yet few data exist for the uptake or sampling rates of polycyclic aromatic hydrocarbons (PAH). Two separate laboratory calibration experiments were conducted to determine the sampling rates of 28 individual PAH and 19 homologues. PAH with a log Kow > 4.5 remained in the linear uptake phase for 30 days, but PAH with a log Kow < 4.5 began to approach steady state within 15 days. Sampling rates, corrected for dissolved organic carbon, ranged from 2.11 to 6.06 L d(-1). Shear flow across the membrane had no statistically significant effect on rates over the range of 0.01-0.50 cm s(-1). Field verification of these sampling rates yielded agreement within about a factor of 2 for most PAH and a factor of 4 for all PAH. The worst agreement was for the most hydrophobic PAH, where partitioning into dissolved and particulate organic carbon pools are more important and less certain. These SPMD sampling rate data will allow quantitative estimations of freely dissolved concentrations of 47 compounds that are commonly used for PAH and petroleum product source identification and allocation.     

Calibrating the uptake kinetics of semipermeable membrane devices in water: impact of hydrodynamics

The use of lipid-containing semipermeable membrane devices (SPMDs) is becoming commonplace, but the potential effects of environmental variables affecting the accumulation of contaminants into SPMDs had not been characterized sufficiently, yet. To characterize the effect of hydrodynamic conditions on the contaminant uptake kinetics, accumulation of pentachlorobenzene, hexachlorobenzene, and hexachlorocyclohexane isomers from water into SPMD was studied at various water flow rates. The accumulation kinetics of hydrophobic compounds (log Kow > 4) are governed by the aqueous boundary layer in linear flow velocity range from 0.06 to 0.28 cm s(-1) and sensitive to slight changes in flow rate. The effect of flow velocity on the exchange kinetics increases with increasing hydrophobicity. Under faster, but still laminar flow conditions (0.28-1.14 cm s(-1)), the sensitivity to changes in flow decreases to a nonsignificant level for the substances under consideration. The results of this study confirm that the use of the laboratory-derived calibration data for estimation of analyte concentrations in the ambient environment is limited unless flow-sensitive performance reference compounds are used.     

Environmental monitoring of hydrophobic organic contaminants: the case of mussels versus semipermeable membrane devices

Concentrations of hydrophobic chemicals in mussels and semipermeable membrane devices (SPMDs) from nine studies published over the past decade, amended with new data obtained in the Scheldt-North Sea area, were assessed to understand the similarities and differences between these sampling matrixes. A model was developed to describe the concentration ratios, using literature values of elimination rate constants and steady-state accumulation factors of both samplers as key parameters. The model could successfully describe the results of seven studies. Differences in concentration ratios among these studies were related to the variability of mussel bioaccumulation factors (BAFs) and water sampling rates of SPMDs. For two studies, the model could only describe the data by adopting unrealistically high water sampling rates, and for one study there were not enough data to test the model. We argue that SPMDs will generally yield more reliable estimates of exposure concentrations than mussels, because in situ BAF values are difficult to estimate, whereas the in situ exchange kinetics of SPMDs can be quantified by measuring the dissipation rates of performance reference compounds. The implications of the results for future and existing monitoring programs are discussed.     

Temperature-dependent uptake rates of nonpolar organic compounds by semipermeable membrane devices and low-density polyethylene membranes

The effect of temperature on sampling rates and sampler-water partition coefficients of semipermeable membrane devices (SPMDs) and low-density polyethylene (LDPE) strips was studied in an experimental setup under controlled flow conditions. Aqueous concentrations of chlorobenzenes, polychlorinated biphenyls (PCBs), and polyaromatic hydrocarbons (PAHs) were maintained by continuous circulation of the water over a generator column. Sampling rates for standard design SPMDs (460 cm2) were in the range of 20-200 L d(-1). No significant differences were observed between sampling rates of SPMDs and LDPE strips, but the latter samplers reached equilibrium faster because of their smaller sorption capacity. Sampling rates at 30 degrees C were higher than at 2 degrees C by a factor of about 3. Sampling rate modeling indicated boundary layer-controlled uptake for compounds with log octanol-water partition coefficients smaller than 4.4 and aqueous boundary-layer controlled uptake for more hydrophobic compounds. SPMD-water partition coefficients did not significantly change with temperature, but LDPE-water partition coefficients were larger at 2 degrees C than at 30 degrees C by a factor of 2. For field application of SPMDs, the results imply that temperature is not a key factor that controls uptake rates unless large geographical and temporal scales are involved. The results confirm that water flow velocity has a profound effect on sampling rates.     

Polycyclic aromatic hydrocarbons in a semiaquatic plant and semipermeable membrane devices exposed to air in Thailand

Semipermeable membrane devices (SPMDs) were deployed at six sites in the Bangkok region, Thailand, to investigate spatial variations in atmospheric concentrations of polycyclic aromatic hydrocarbons (PAHs). Sampling sites affected by various levels of traffic intensity were studied. In addition, PAH levels were determined in a common human food plant (water spinach) harvested from canals and ponds in the sampling areas. Significant differences in atmospheric PAH concentrations between sites were found, with 10 times higher PAH levels in the urban areas compared to the rural areas. Increasing concentrations of 1-methylphenanthrene relative to phenanthrene were found in the urban air close to the city center, indicating that traffic probably contributed to the higher PAH concentrations detected. Due to SPMD's passive sampling technique, their long-term operation and high ability to detect spatial differences, they proved to be suitable for semiquantitative field studies of PAHs. The PAH compounds sampled with SPMDs were mainly associated with gaseous PAHs, while both gas phase and particle-bound PAHs were detected in the plant samples. The relative abundance ratios of some PAHs in the plants were not well correlated with the ratios detected in the SPMDs, indicating that gas-phase exposure made low contribution to the PAH concentrations in the plants. However, similarities in the profiles of 3-ring PAHs between the SPMD and plant samples indicate that gas-phase exchange occurs between the atmosphere and the plants.     

Passive air sampling using semipermeable membrane devices at different wind-speeds in situ calibrated by performance reference compounds

Semipermeable membrane devices (SPMDs) are passive samplers used to measure the vapor phase of organic pollutants in air. This study tested whether extremely high wind-speeds during a 21-day sampling increased the sampling rates of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs), and whether the release of performance reference compounds (PRCs) was related to the uptakes at different wind-speeds. Five samplers were deployed in an indoor, unheated, and dark wind tunnel with different wind-speeds at each site (6-50 m s(-1)). In addition, one sampler was deployed outside the wind tunnel and one outside the building. To test whether a sampler, designed to reduce the wind-speeds, decreased the uptake and release rates, each sampler in the wind tunnel included two SPMDs positioned inside a protective device and one unprotected SPMD outside the device. The highest amounts of PAHs and PCBs were found in the SPMDs exposed to the assumed highest wind-speeds. Thus, the SPMD sampling rates increased with increasing wind-speeds, indicating that the uptake was largely controlled by the boundary layer at the membrane-air interface. The coefficient of variance (introduced by the 21-day sampling and the chemical analysis) for the air concentrations of three PAHs and three PCBs, calculated using the PRC data, was 28-46%. Thus, the PRCs had a high ability to predict site effects of wind and assess the actual sampling situation. Comparison between protected and unprotected SPMDs showed that the sampler design reduced the wind-speed inside the devices and thereby the uptake and release rates.     

Estimation of the uptake rate constants for polycyclic aromatic hydrocarbons accumulated by semipermeable membrane devices and triolein-embedded cellulose acetate membranes

In this paper we report an extension of our previous work on the triolein-embedded cellulose acetate membrane (TECAM) as a passive sampling device (PSD) and describe the results from simultaneous exposure of TECAMs and triolein-containing semipermeable membrane devices (SPMDs) to PAHs in lake water for 16 days. The data obtained provided a comparison of the uptake rates of specific PAHs by the two PSDs. Using 16-day accumulation tests, similar PAH distribution patterns in TECAMs and in SPMDs (R2 = 0.89, p < 0.0001) were observed. However, it was noted that TECAMs could take up greater amounts of PAHs than SPMDs (735 ng/g of TECAM vs 630 ng/g of SPMD). Uptake rate constants of TECAMs and SPMDs for 16 priority pollutant (PP) PAHs, corrected for dissolved organic carbon, ranged from 0.28 to 2.94 L d(-1) and from 0.16 to 0.91 L d(-1), respectively. The elimination rate constants of TECAMs were 1.4-6.7 times greater than those observed for SPMDs, thereby indicating that PAHs required shorter times to achieve equilibrium in TECAMs than in SPMDs. Thus, the results of the present study suggest that TECAMs have significant potential as a good monitor to assess the pollution of hydrophobic pollutants in aquatic environments.     

Coupling effects during steady-state solute diffusion through a semipermeable clay membrane

Two separate coupling effects are evaluated with respect to steady-state potassium chloride (KCl) diffusion through a bentonite-based geosynthetic clay liner (GCL) that behaves as a semipermeable membrane. Both of the coupling effects are correlated with measured chemico-osmotic efficiency coefficients, omega, that range from 0.14 to 0.63 for the GCL. The first coupling effect is an explicit (theoretical) salt-sieving effect expressed as a coupled effective salt diffusion coefficient, Domega*, that is lower than the true (uncoupled) effective salt diffusion coefficient, Ds*, because of the observed membrane behavior. However, the maximum difference between Domega* and Ds* based on measured chloride concentrations is relatively small (i.e., = 10%), and the difference decreases with decreasing omega (i.e., Domega* --> Ds* as omega --> 0). The second coupling effect is implicit (empirical) and is characterized by the measurement of concentration-dependent effective salt diffusion coefficients that results in an degrees 300% decrease in Ds* as omega increases from 0.14 to 0.63. The decrease in Ds* resulting from implicit coupling is attributed to solute exclusion described in terms of a restrictive tortuosity factor.     

Performance of a household-level arsenic removal system during 4-month deployments in Bangladesh

A simple arsenic removal system was used in Bangladesh by six households for 4 months to treat well water containing 190-750 microg/L As as well as 0.4-20 mg/L Fe and 0.2-1.9 mg/L P. The system removes As from a 16-L batch of water in a bucket by filtration through a sand bed following the addition of about 1.5 g of ferric sulfate and 0.5 g of calcium hypochlorite. Arsenic concentrations in all but 1 of 72 samples of treated water were below the Bangladesh drinking water standard of 50 microg/L for As. Approximately half of the samples also met the World Health Organization (WHO) guideline of 10 microg/L. At the two wells that did not meet the WHO guideline, observations were confirmed by additional experiments in one case ([P] = 1.9 mg/L) but not in the other, suggesting that the latter household was probably not following the instructions. Observed residual As levels are consistent with predictions from a surface complexation model only if the site density is increased to 2 mol/mol of Fe. With the exception of Mn, the average concentrations of other inorganic constituents of health concern (Cr, Ni, Cu, Se, Mo, Cd, Sb, Ba, Hg, Pb, and U) in treated water were below their respective WHO guideline for drinking water.     

Spectrofluorimetric assessment of bacterial cell membrane damage by pulsed electric field

A rapid fluorescence staining technique was used to assess cell membrane damage and ensuing injury and death caused by pulsed electric field (PEF) treatment. Cell suspensions of Lactobacillus leichmannii ATCC 4797, Listeria monocytogenes Scott A and Escherichia coli O157:H7 ATCC 35150 were subjected to PEF for145.6 μs at field strengths of 5–20 kV/cm. Immediately after PEF treatment, cells were stained with propidium iodide (PI), and changes in fluorescence intensity were measured with a spectrofluorimeter. Increase in field strength decreased the count of survivors and proportionally increased the fluorescence intensity, confirming that cell inactivation by PEF is caused by membrane damage. Cells of E. coli O157:H7 were incubated with or without EDTA before exposure to PEF, but similar inactivation was observed, regardless of the EDTA pre-treatment. Increase in the fluorescence intensity, however, was appreciable in the EDTA-PEF-treated cells. The fluorescence staining technique, therefore, revealed membrane-related injury when EDTA pre-treated cells were PEF-treated. In conclusion, the fluorescence staining technique can be used to assess membrane damage associated with PEF treatments and is potentially useful in determining the relative sensitivity of microorganisms to PEF or monitoring the efficacy of such treatments.     

Visualization of results from genomic evaluations

Genomic predictions of estimated breeding values (EBV) for dairy cattle include effects of tens of thousands of markers distributed over 30 chromosomes for many traits. There are so many numbers that data are difficult to compare, levels of detail are obscured, and data cannot easily be tabulated. Well-designed graphics can present more information in a smaller area than text or tables and provide insight into the data. Subtle differences can be detected more easily among graphics than among data grids, allowing information to be presented with greater density. Genomic data can be visualized at several levels, such as the distribution of marker effects across the genome and relationships among markers on the same chromosome. All markers affecting a trait can be plotted on the same ordinate to visualize the distribution of marker effects across the genome, colors or textures can be used to differentiate between chromosomes, and stacked graphs can be constructed to compare interesting groups of traits. Chromosomal EBV can be presented as high-resolution graphics embedded in text to provide an overview of individual animals for comparison to potential mates. Small multiples of chromosomal genetic correlation matrices from which nonsignificant values have been excluded can be used to identify interesting patterns of association among traits, such as that on chromosome 18 associated with calving traits, conformation, and economic merit. Line plots of marker effects for recessive traits can be used to quickly locate chromosomal regions in which causative mutations are probably located, identifying areas of interest for further study. These graphics are easily produced automatically and added to online query systems, providing users with novel information at little cost.     

XRF-analysis of fine and ultrafine particles emitted from laser printing devices

In this work, the elemental composition of fine and ultrafine particles emitted by ten different laser printing devices (LPD) is examined. The particle number concentration time series was measured as well as the particle size distributions. In parallel, emitted particles were size-selectively sampled with a cascade impactor and subsequently analyzed by the means of XRF. In order to identify potential sources for the aerosol's elemental composition, materials involved in the printing process such as toner, paper, and structural components of the printer were also analyzed. While the majority of particle emissions from laser printers are known to consist of recondensated semi volatile organic compounds, elemental analysis identifies Si, S, Cl, Ca, Ti, Cr, and Fe as well as traces of Ni and Zn in different size fractions of the aerosols. These elements can mainly be assigned to contributions from toner and paper. The detection of elements that are likely to be present in inorganic compounds is in good agreement with the measurement of nonvolatile particles. Quantitative measurements of solid particles at 400 °C resulted in residues of 1.6 × 10(9) and 1.5 × 10(10) particles per print job, representing fractions of 0.2% and 1.9% of the total number of emitted particles at room temperature. In combination with the XRF results it is concluded that solid inorganic particles contribute to LPD emissions in measurable quantities. Furthermore, for the first time Br was detected in significant concentrations in the aerosol emitted from two LPD. The analysis of several possible sources identified the plastic housings of the fuser units as main sources due to substantial Br concentrations related to brominated flame retardants.     

Factors affecting milk flow traits in dairy cows: results of a field study

The study of milk flow curves provides useful information for enhancing milking efficiency and protecting udder health by adapting milking machine and milking procedures to the physiological requirements of the cow. The aim of this experiment was to investigate, using field data, the relationships among traits of the milk flow curves, their sources of variation, and milking performances in terms of milk production, machine-on time, and udder health. A total of 2,486 milk flow curves of the whole udder were collected in 82 Italian Holstein-Friesian dairy herds in the Lombardy region of Italy. Approximately one-third (35.1%) of milk flow curves were classified as bimodal. Most flow characteristics were influenced by lactation number, days in milk, and peak flow but also strongly affected by premilking operations. Proper udder preparation, including forestripping and predipping, resulted in better milking performances compared with poor preparation, with greater milk yield per milking, shorter milking time, and lesser bimodality. Premilking delay time, between the start of teat stimulation and cup attachment, affected milking time significantly: The shortest milking time was obtained for a range of delay time between 1 and 60 s. As the delay time increased, the percentage of bimodality dropped significantly. Increasing the number of clusters per operator led to greater percentages of bimodal curves. The greater somatic cell count of cows with bimodal curves supports the hypothesis of the negative effect of bimodality on udder health and indicates the importance of avoiding its occurrence using proper pre-milking procedures.     

乳化液膜法提取废水中柠檬酸膜配方的研究

利用恒界面反应器，考察了流动载体，流动载体浓度，表面活性剂浓度。内相试剂浓度。制乳转速，油内比等因素对提取率的影响。用正交试验法设计实验。结果表明：在恒界面情况下，载体采用3%（V/V）三正辛胺（TOA），表面活性剂采用3%（V/V）span80。内相采用浓度为15%（W/V）Na2CO3，油内比Roi为1：1，制乳转速n=2000r/min是该实验液膜体系的较佳配方。     

Wheat quality in organic and conventional farming: results of a 21 year field experiment

Consumers have become more aware of healthy and safe food produced with low environmental impact. Organic agriculture is of particular interest in this respect, as manifested by 5.768 million hectares managed pursuant to Council Regulation (EEC) 2092/91 in Europe. However, there can be a considerable risk that the avoidance of chemical inputs in organic farming will result in poor food quality. Here the results of a study on the quality of wheat (Triticum aestivum L.) grown in a 21 year agrosystem comparison between organic and conventional farming in central Europe are reported. Wheat was grown in a ley (grass/clover) rotation. The 71% lower addition of plant‐available nitrogen and the reduced input of other means of production to the organic field plots led to 14% lower wheat yields. However, nutritional value (protein content, amino acid composition and mineral and trace element contents) and baking quality were not affected by the farming systems. Despite exclusion of fungicides from the organic production systems, the quantities of mycotoxins detected in wheat grains were low in all systems and did not differ. In food preference tests, as an integrative method, rats significantly preferred organically over conventionally produced wheat. The findings indicate that high wheat quality in organic farming is achievable by lower inputs, thereby safeguarding natural resources. Copyright © 2007 Society of Chemical Industry     

Application of an ultrasound field in chemical cleaning of ceramic tubular membrane fouled with whey proteins

Chemical cleaning of a severe in-pore-fouling may be improved by applying an ultrasound (US) field in a cleaning-in-place (CIP) system, under both the batch and flow conditions. This study is concerned with the cleaning of a 200-nm ceramic membrane, fouled with whey proteins, in an US field of relatively low frequency of 35 kHz, without applying a transmembrane pressure (TMP) and cross-flow velocity. Two types of cleaning agent solutions of different concentrations were applied: alkali (NaOH) and a mixture of commercial detergents (P3-Ultrasil 67 and 69) at a sonication time of 30 min. It was found that the application of US was less effective in the combination with sodium hydroxide than with the mixture of commercial detergents. Using US in a mixture of 0.25% w/w P3-Ultrasil 67 and 0.4% w/w P3-Ultrasil 69 resulted in the highest flux recovery of 86.5 ± 2.9%, after 30 min of sonication, and produced an overall efficiency of 96.3 ± 0.4%, after the second sonication. It was concluded that the application of the US field in a batch mode, combined with the mentioned chemical agents, can significantly improve the cleaning efficiency.     

利用雷达海面回波谱获取海风信息

利用雷达多波束采样法确定唯一合理的风向,再利用有效浪高及浪高谱峰值频率,由SMB算法或JONSWAP算法精确计算风速,从而得到完整的海面风场信息.