Sorption to black carbon of organic compounds with varying polarity and planarity

It is becoming increasingly clear that the products of incomplete combustion (soot and charcoal, collectively termed black carbon or BC) can be responsible for as much as 80 - 90% of the total sorption to sediments of aromatic, planar, and hydrophobic compounds such as polycyclic aromatic hydrocarbons or planar polychlorinated biphenyls. In the present study, it was investigated whether a nonpolar aliphatic compound (hexachloroethane) and three nonplanar bipolar compounds with different functional groups [free electron pairs but no aromatic ring (butylate) or free electron pairs and an aromatic ring (diuron, atrazine)] would also show strong and nonlinear sorption to a BC-enriched sediment. At a concentration of 1 ng/L, the extent of elevated BC sorption compared to total organic carbon (TOC) sorption increased in the order atrazine < hexachloroethane < butylate < diuron. Rationalization of the differences between the sorbates was attempted in terms of dispersive and steric effects. This study shows that the effects of strong BC sorption apply to a broader range of organic contaminants than previously thought, and the results will aid in a better understanding of BC sorption mechanisms and improved fate modeling of contaminants in the environment.     

Differentiation of apple juice samples on the basis of heat treatment and variety using chemometric analysis of MIR and NIR data

The potential of mid-infrared (MIR) and near-infrared (NIR) spectroscopy for their ability to differentiate between apple juice samples on the basis of apple variety and applied heat-treatment was evaluated. The heat-treatment involved exposure of juice samples (15 ml) for 30 s in a 900 W microwave oven and the apple varieties used to produce the juice samples were Bramley, Elstar, Golden Delicious and Jonagold. The chemometric procedures applied to the MIR and NIR data were partial least squares regression (PLS1 for differentiation on the basis of heat-treatment, PLS2 for varietal differentiation) and linear discriminant analysis (LDA) applied to principal component (PC) scores. PLS1 and PLS2 gave the highest level of correct classification of the apple juice samples according to heat-treatment (77.2% for both MIR and NIR data) and variety (78.3–100% for MIR data; 82.4–100% for NIR data), respectively.     

The potential of NIR spectroscopy for the detection of the adulteration of orange juice

Near-infrared spectroscopy was used to investigate the adulteration of 65 authentic concentrated orange juice samples obtained from Brazil and Israel. These samples were adulterated with 100 g kg^?1 additions (ie 100 g added to 900 g) of (1) orange pulpwash, (2) grapefruit juice, and (3) a synthetic sugar/acid mixture and with 50 g kg^?1 additions (ie 50 g added to 950 g) of (4) orange pulpwash, and (5) grapefruit juice. All samples were scanned on the NIR systems 6500 spectrophotometer over the 1100-2498 nm wavelength range. Principal component analysis was used to reduce each spectrum to 20 principal components. Factorial discriminant analysis was used to distinguish between the different sample groups. Using orange juice and orange juice adulterated at the 100 g kg^?1 level, accurate classification rates of 94–95% were obtained. To classify samples adulterated at the 50 g kg^?1 level, the calibration development sample set had to be augmented by the inclusion of samples adulterated at this lower level—after this augmentation, an accurate classification rate of 94% was obtained. The results demonstrated that the application of principal component and factorial discriminate analysis to NIR reflectance spectra can detect the adulteration of orange juice with an average accuracy of 90%. Furthermore, not one adulterated sample was predicted as being an authentic orange juice throughout the entire test regime.     

Dietary supplement for energy and reduced appetite containing the β-agonist isopropyloctopamine leads to heart problems and hospitalisations

In 2013 the Dutch authorities issued a warning against a dietary supplement that was linked to 11 reported adverse reactions, including heart problems and in one case even a cardiac arrest. In the UK a 20-year-old woman, said to have overdosed on this supplement, died. Since according to the label the product was a herbal mixture, initial LC-MS/MS analysis focused on the detection of plant toxins. Yohimbe alkaloids, which are not allowed to be present in herbal preparations according to Dutch legislation, were found at relatively high levels (400–900 mg kg^–1). However, their presence did not explain the adverse health effects reported. Based on these effects the supplement was screened for the presence of a β-agonist, using three different biosensor assays, i.e. the validated competitive radioligand β2-adrenergic receptor binding assay, a validated β-agonists ELISA and a newly developed multiplex microsphere (bead)-based β-agonist assay with imaging detection (MAGPIX^®). The high responses obtained in these three biosensors suggested strongly the presence of a β-agonist. Inspection of the label indicated the presence of N-isopropyloctopamine. A pure standard of this compound was bought and shown to have a strong activity in the three biosensor assays. Analysis by LC-full-scan high-resolution MS confirmed the presence of this ‘unknown known’ β3-agonist N-isopropyloctopamine, reported to lead to heart problems at high doses. A confirmatory quantitative analysis revealed that one dose of the preparation resulted in an intake of 40–60 mg, which is within the therapeutic range of this compound. The case shows the strength of combining bioassays with chemical analytical techniques for identification of illegal pharmacologically active substances in food supplements.     

Land use regression model for ultrafine particles in Amsterdam

There are currently no epidemiological studies on health effects of long-term exposure to ultrafine particles (UFP), largely because data on spatial exposure contrasts for UFP is lacking. The objective of this study was to develop a land use regression (LUR) model for UFP in the city of Amsterdam. Total particle number concentrations (PNC), PM10, PM2.5, and its soot content were measured directly outside 50 homes spread over the city of Amsterdam. Each home was measured during one week. Continuous measurements at a central urban background site were used to adjust the average concentration for temporal variation. Predictor variables (traffic, address density, land use) were obtained using geographic information systems. A model including the product of traffic intensity and the inverse distance to the nearest road squared, address density, and location near the port explained 67% of the variability in measured PNC. LUR models for PM2.5, soot, and coarse particles (PM10, PM2.5) explained 57%, 76%, and 37% of the variability in measured concentrations. Predictions from the PNC model correlated highly with predictions from LUR models for PM2.5, soot, and coarse particles. A LUR model for PNC has been developed, with similar validity as previous models for more commonly measured pollutants.     

Evolution of the localisation and composition of phenolics in grape skin between veraison and maturity in relation to water availability and some climatic conditions

BACKGROUND: Several studies have investigated the composition of phenolics in grape skin during grape maturation under various conditions of light exposure, water stress, nitrogen supply and mineral nutrition, but their localisation during berry development is not well known. In this study the composition and localisation of proanthocyanidins were monitored for three years on four plots known to induce a distinctive behaviour of the vine (Cabernet Franc). The composition of phenolics was determined by spectrophotometry; also, in one year, proanthocyanidins were determined by high‐performance liquid chromatography. Further information was obtained histochemically by means of toluidine blue O staining and image analysis. RESULTS: The results indicated that clear differences in phenolic quantification existed between the biochemical and histochemical approaches; the proportion of cells without phenolics was not linked with the quantity determined by the analytical methods used. The histochemical method showed the evolution of the localisation and typology of cells with and without phenolics during ripening. The number of cells without any phenolic compounds appeared to be very dependent on the mesoclimatic conditions and only slightly dependent on the site water status. CONCLUSION: Clear differences in phenolic quantification existed between the biochemical and histochemical approaches; the proportion of cells with phenolics was not linked with the quantity determined by biochemistry. The histochemical method showed an evolution of the localisation and typology of cells with and without phenolics in which mesoclimatic conditions were the most influential factor. Finally, the study showed some advantages of the histochemical approach: it gives information about the anatomy of the tissue as well as the nature and distribution of some of the large macromolecules and allows reconstruction of the three‐dimensional plant structure. Copyright © 2011 Society of Chemical Industry     

Determination of the sources of indoor PM2.5 in Amsterdam and Helsinki

Daily PM2.5 samples were repeatedly collected (1-8 times) in the homes of elderly nonsmoking individuals with coronary heart disease in Amsterdam, The Netherlands (33 individuals) and Helsinki, Finland (44 individuals). Sources of indoor PM2.5 were evaluated using a two-way multilinear engine model. Because the indoor elemental data lacked a traffic marker, separation of traffic related PM was attempted by combining the indoor data with fixed site outdoor data that also contained NO. Six outdoor sources, including long-range transport (LRT), urban mixture, oil combustion, traffic, sea-salt, and soil were identified, and three indoor sources were resolved: resuspension, potassium-rich and copper-rich sources. The average contribution of the indoor factors was 6% (1.1 microg m(-3)) and 22% (2.4 microg m(-3)) in Amsterdam and Helsinki, respectively. The highest longitudinal correlations between source-specific outdoor and indoor PM2.5 concentrations were found for LRT and urban mixture; the median R was above 0.6 for most sources. The longitudinal correlations were lower in Helsinki than in Amsterdam. Indoor-generated PM2.5 was not related to ambient concentrations. We conclude that using outdoor and indoor data together improved the source apportionment of indoor PM2.5. The results support the use of fixed site outdoor measurements in epidemiological time-series studies on outdoor air pollution.     

Validity of residential traffic intensity as an estimate of long-term personal exposure to traffic-related air pollution among adults

The validity of traffic intensity near the home as an estimate for the personal long-term exposure to traffic-related air pollution in an adult population was tested. Personal and near-home outdoor exposure to PM2.5, soot, NO, NO2, and NOx was monitored four to five times during 48 h periods in older adults. A group of 23 participants lived in high traffic intensity streets (>10000 vehicles/(24 h)), and 22 lived in low traffic intensity streets. The relation between average personal exposure and traffic intensity at the residential address was explored by taking indoor sources into account. Large differences in the measured outdoor concentrations between locations in high traffic and low traffic intensity streets were found for soot (68%), NO (127%), and NOx (35%). Differences were smaller for PM2.5 (14%) and NO2 (22%). Slightly elevated ratios were found for personal exposure to soot (1.15; 95% confidence interval (CI), 1.01-1.30)when comparing adults living in high traffic intensity streets with adults living in low traffic intensity streets. For NO, increased personal exposure (1.16) was seen for the same comparison, but this difference failed to reach statistical significance (CI, 0.80-1.66). Traffic intensity on the street of residence predicted personal exposure to soot but not to PM2.5 or nitrogen oxides. Traffic intensity may not correlate well to personal exposure and accordingly substantial misclassification of exposure may occur when traffic intensity is used as an exposure indicator in epidemiological studies. Time spent in traffic and spending time outdoors were associated with increased personal exposure of soot and PM2.5, but not NOx.     

Relations between environmental black carbon sorption and geochemical sorbent characteristics

Pyrogenic carbon particles in sediments (soot and charcoal, collectively termed "black carbon" or BC) appear to be efficient sorbents of many hydrophobic organic compounds, so they may play an important role in the fate and toxicity of these substances. To properly model toxicant sorption behavior, it is important to (i) quantify the magnitude of the role of BC in sorption and (ii) elucidate which geochemical BC characteristics determine the strength of environmental BC sorption. Sorption isotherms of d10-phenanthrene (d10-PHE) were determined over a wide concentration range (0.0003-20 microg/L), for five sediments with widely varying characteristics. From the sorption isotherms, we determined Freundlich coefficients of environmental BC sorption, K(F,BCenv. These varied from 10(4.7) to 10(5.5). From the data, it could be deduced that BC was responsible for 49-85% of the total d10-PHE sorption at a concentration of 1 ng/L. At higher concentrations, the importance of BC for the sorption process diminished to <20% at 1 microg/L and 0-1% at 1 mg/L. There were no significant relationships between BC sorption strength and the tested geochemical BC characteristics [the fraction of small (<38 microm) BC particles, the BC resistance to high-temperature oxidation, the fraction of biomass-derived BC, the native polycyclic aromatic hydrocarbon and total organic carbon contents]. Because of the limited variation in BC sorption strength with widely varying BC characteristics, the presented BC sorption coefficients may putatively be used as generic starting points for environmental modeling purposes.     

Sorption of phenanthrene to environmental black carbon in sediment with and without organic matter and native sorbates

Strong sorption to soot- and charcoal-like material (collectively termed black carbon or BC) in soils and sediments is possibly the reason for recent observations of elevated geosorbent-water distribution ratios, slow desorption, limited uptake, and restricted bioremediation. We evaluated the role of environmental BC in the sorption of phenanthrene (PHE) to a polluted lake sediment from a Rhine River sedimentation area. Sorption isotherms were determined over a wide concentration range (0.0005-6 microg/ L) for the original sediment (with organic matter or OM, native sorbates, and BC), sediment from which we had stripped > 90% of the native sorbates (only OM and BC), and sediment combusted at 375 degrees C (only BC). The sorption isotherms of the original and stripped sediments were almost linear (Freundlich coefficient or n(F) > 0.9), whereas the isotherm of the BC remaining after the sediment combustion was highly nonlinear (n(F) = 0.54). At low concentrations (ng/L range), PHE sorption to BC in the combusted sediment was found to exceed the total PHE sorption in the original and stripped sediments. This implies that it may not be possible to use a BC-water sorption coefficient measured in combusted sediment to estimate total sorption to the original sediment. This "intrinsic" BC-water sorption coefficient after combustion was calculated to be 9 times larger than the "environmental" one in the untreated sediment. Competition between the added PHE and the native PAHs and/or OM may explain this difference. It appears that, at low aqueous PHE concentrations (ng/L and below), BC is the most important geosorbent constituent with respect to sorption. At higher concentrations (microg/L), BC sorption sites become saturated and BC sorption is overwhelmed by sorption to the other OM constituents. Because sorption is a central process affecting contaminant behavior and ecotoxicity, understanding this process can strongly contribute to risk assessment and fate modeling.