Impact of treatment processes on the removal of perfluoroalkyl acids from the drinking water production chain

The behavior of polyfluoralkyl acids (PFAAs) from intake (raw source water) to finished drinking water was assessed by taking samples from influent and effluent of the several treatment steps used in a drinking water production chain. These consisted of intake, coagulation, rapid sand filtration, dune passage, aeration, rapid sand filtration, ozonation, pellet softening, granular activated carbon (GAC) filtration, slow sand filtration, and finished drinking water. In the intake water taken from the Lek canal (a tributary of the river Rhine), the most abundant PFAA were PFBA (perfluorobutanoic acid), PFBS (perfluorobutane sulfonate), PFOS (perfluorooctane sulfonate), and PFOA (perfluorooctanoic acid). During treatment, longer chain PFAA such as PFNA (perfluorononanoic acid) and PFOS were readily removed by the GAC treatment step and their GAC effluent concentrations were reduced to levels below the limits of quantitation (LOQ) (0.23 and 0.24 ng/L for PFOS and PFNA, respectively). However, more hydrophilic shorter chain PFAA (especially PFBA and PFBS) were not removed by GAC and their concentrations remained constant through treatment. A decreasing removal capacity of the GAC was observed with increasing carbon loading and with decreasing carbon chain length of the PFAAs. This study shows that none of the treatment steps, including softening processes, are effective for PFAA removal, except for GAC filtration. GAC can effectively remove certain PFAA from the drinking water cycle.The enrichment of branched PFOS and PFOA isomers relative to non branched isomers during GAC filtration was observed during treatment. The finished water contained 26 and 19 ng/L of PFBA and PFBS. Other PFAAs were present in concentrations below 4.2 ng/L The concentrations of PFAA observed in finished waters are no reason for concern for human health as margins to existing guidelines are sufficiently large.     

Consumption of Hibiscus sabdariffa L. aqueous extract and its impact on systemic antioxidant potential in healthy subjects

BACKGROUND: To evaluate health benefits attributed to Hibiscus sabdariffa L. a randomized, open‐label, two‐way crossover study was undertaken to compare the impact of an aqueous H. sabdariffa L. extract (HSE) on the systemic antioxidant potential (AOP; assayed by ferric reducing antioxidant power (FRAP)) with a reference treatment (water) in eight healthy volunteers. The biokinetic variables were the areas under the curve (AUC) of plasma FRAP, ascorbic acid and urate that are above the pre‐dose concentration, and the amounts excreted into urine within 24 h (Ae_0–24) of antioxidants as assayed by FRAP, ascorbic acid, uric acid, malondialdehyde (biomarker for oxidative stress), and hippuric acid (metabolite and potential biomarker for total polyphenol intake). RESULTS: HSE caused significantly higher plasma AUC of FRAP, an increase in Ae_0–24 of FRAP, ascorbic acid and hippuric acid, whereas malondialdehyde excretion was reduced. Furthermore, the main hibiscus anthocyanins as well as one glucuronide conjugate could be quantified in the volunteers' urine (0.02% of the administered dose). CONCLUSION: The aqueous HSE investigated in this study enhanced the systemic AOP and reduced the oxidative stress in humans. Furthermore, the increased urinary hippuric acid excretion after HSE consumption indicates a high biotransformation of the ingested HSE polyphenols, most likely caused by the colonic microbiota. Copyright © 2012 Society of Chemical Industry     

Cost-effective CO2 emission reduction through heat,power and biofuel production from woody biomass: A spatially explicit comparison of conversion technologies

Bioenergy is regarded as cost-effective option to reduce CO₂ emissions from fossil fuel combustion. Among newly developed biomass conversion technologies are biomass integrated gas combined cycle plants (BIGCC) as well as ethanol and methanol production based on woody biomass feedstock. Furthermore, bioenergy systems with carbon capture and storage (BECS) may allow negative CO₂ emissions in the future. It is still not clear which woody biomass conversion technology reduces fossil CO₂ emissions at least costs. This article presents a spatial explicit optimization model that assesses new biomass conversion technologies for fuel, heat and power production and compares them with woody pellets for heat production in Austria. The spatial distributions of biomass supply and energy demand have significant impact on the total supply costs of alternative bioenergy systems and are therefore included in the modeling process. Many model parameters that describe new bioenergy technologies are uncertain, because some of the technologies are not commercially developed yet. Monte-Carlo simulations are used to analyze model parameter uncertainty. Model results show that heat production with pellets is to be preferred over BIGCC at low carbon prices while BECS is cost-effective to reduce CO₂ emissions at higher carbon prices. Fuel production – methanol as well as ethanol – reduces less CO₂ emissions and is therefore less cost-effective in reducing CO₂ emissions.     

A SIMULATION OF A MOTIONLESS MIXER

Continuous laminar mixing in segmented twisted-tape motionless mixers is considered. A solution to the steady isothermal creeping flow of a Newtonian fluid in a twisted-tape mixer has been obtained via two-dimensional numerical procedures. The developed flow within a section of the mixer has been solved in a helical coordinate system by an iterative scheme. The resulting solution is rigorously correct in the absence of entrance and exit flows at the junction between sections. An algorithm is presented for the modelling of these junction flows via two-dimensional procedures. Simulated cross-sectional mixing patterns have been generated for comparison with experimental results

The performance of twisted-tape mixers is simulated for various designs, beginning with the particular geometry of the Kcnics Static Mixer, and for different operating conditions Results suggest that the rate of mixing as a function of the total twist per section is optimized with respect to pressure drop when sections contain 80 degrees of twist. The capability for rational improvement in other design and operating parameters is illustrated. The mechanisms of laminar mixing are discussed and quantified; of primary importance is the tendency for interfacial area to assume an orientation within each section which is favorable to mixing in subsequent sections.     

Chemical investigation of eight different types of carbonaceous particles using thermoanalytical techniques

The chemical composition of ambient aerosol particles affects numerous important aerosol parameters such as their hygroscopicity, optics, and mass as well as their potentially adverse health effects. The objective of this study was to derive both detailed chemical speciation and useful proxies for the quantitative classification of the organic matter (OM) content of carbonaceous aerosol samples. Using three different thermal desorption techniques in an inert atmosphere we investigated eight different carbonaceous particulate matter (PM) samples used for health effect studies: thermal desorption gas chromatography with mass spectrometry, evolved gas analysis with mass spectrometry, and thermogravimetry with Fourier transform infrared spectroscopy. The samples include different types of laboratory-generated particles (pigment black, diffusion flame soot, spark-generated carbon) and two ambient aerosol samples (diesel soot and particulates collected in a road tunnel). All samples showed increasing mass desorption with rising temperature, but no reliable OM classification was possible based on thermal mass desorption alone. In fact, the "organic-free" spark-generated carbon particles showed the second highest mass desorption at 800 degrees C due to the formation of oxygenated structures on unsaturated surface sites and the subsequent evolution of CO and CO2 at elevated temperatures. A quantitative OM classification was accomplished by combining measurements of thermogravimetry and mass spectrometry (up to 800 degrees C) into a novel parameter, the "apparent organic mass fraction". The validity of this classification was confirmed with a second proxy parameter, based only on the evolution of organic components during thermal desorption and information on the generation process of the particles. Both types of pigment blacks (Printex) samples and the spark-generated carbon particles showed the lowest apparent organic mass fraction (< 5%), whereas for road tunnel and diesel emission particles < 16 and < 19% was estimated, respectively.     

Comparison of analytical techniques for dynamic trace metal speciation in natural freshwaters

Several techniques for speciation analysis of Cu, Zn, Cd, Pb, and Ni are used in freshwater systems and compared with respect to their performance and to the metal species detected. The analytical techniques comprise the following: (i) diffusion gradients in thin-film gels (DGT); (ii) gel integrated microelectrodes combined to voltammetric in situ profiling system (GIME-VIP); (iii) stripping chronopotentiometry (SCP); (iv) flow-through and hollow fiber permeation liquid membranes (FTPLM and HFPLM); (v) Donnan membrane technique (DMT); (vi) competitive ligand-exchange/stripping voltammetry (CLE-SV). All methods could be used both under hardwater and under softwater conditions, although in some cases problems with detection limits were encountered at the low total concentrations. The detected Cu, Cd, and Pb concentrations decreased in the order DGT > or = GIME-VIP > or = FTPLM > or = HFPLM approximately = DMT (>CLE-SV for Cd), detected Zn decreased as DGT > or = GIME-VIP and Ni as DGT > DMT, in agreement with the known dynamic features of these techniques. Techniques involving in situ measurements (GIME-VIP) or in situ exposure (DGT, DMT, and HFPLM) appear to be appropriate in avoiding artifacts which may occur during sampling and sample handling.     

Detection of DNA-bound advanced glycation end-products by immunoaffinity chromatography coupled to HPLC-diode array detection

Sugars and sugar degradation products are formed during food processing, but also endogenously in vivo. In vitro, nucleosides and DNA react readily with these carbonyl compounds during the formation of the two diastereomers of N(2)-carboxyethyl-2'-deoxyguanosine (CEdG(A,B)), leading to a loss of DNA integrity. Only little is known about DNA glycation in vivo and about the influence of nutrition on CEdG formation. In this study, we developed a sensitive method to analyze DNA glycation by HPLC. For this purpose, immunoaffinity chromatography (IAC) using a polyclonal antibody against N(2)-carboxyethylguanine (CEguanine) was coupled to HPLC-DAD. In some samples, peak identity was confirmed by LC-MS/MS. The recovery of CEguanine from the IAC columns was 52.5% +/- 3.6 (n = 4). Thus, it was possible for the first time to detect CEdG(A,B), N(2)-carboxyethylguanosine (CEG(A,B)), and CEguanine in 11 human urine samples. However, due to imprecision of IAC, valid quantification of the adducts could not be achieved. Furthermore, CEdG was also detected in the DNA of cultured human smooth muscle cells (SMCs) and bovine aorta endothelium cells (BAECs). In BAECs, CEdG(A,B) were found by HPLC-DAD and LC-MS/MS after immunoaffinity purification, whereas in SMCs DNA-advanced glycation end-products were only detected with the more sensitive LC-MS/MS method.     

Influence of EDDS on metal speciation in soil extracts: measurement and mechanistic multicomponent modeling

The use of the [S,S]-isomer of EDDS to enhance phytoextraction has been proposed for the remediation of heavy metal contaminated soils. Speciation of metals in soil solution in the presence of EDDS and dissolved organic matter (DOM) received, however, almost no attention, whereas metal speciation plays an important role in relation to uptake of metals by plants. We investigated the influence of EDDS on speciation of dissolved metals in batch extraction experiments using fourfield-contaminated soils with pH varying between 4.7 and 7.2. Free metal concentrations were determined with the Donnan membrane technique, and compared with results obtained with the chemical speciation program ECOSAT and the NICA-Donnan model using a multicomponent approach. Addition of EDDS increased total metal concentrations in our soil extracts by a factor between 1.1 and 32 (Al), 2.1-48 (Cu), 1.1-109 (Fe), 1.1-5.5 (Ni), and 1.3-17 (Zn). In general, Al, Cu, Fe, and Zn had the largest total concentrations in the EDDS-treated extracts, but the contribution of these metals to the sum of total metal concentrations varied significantly between our soils. Free metal concentrations varied between 7.0 and 8.9 (pCd2+), 3.9-9.9 (pCu2+), 6.3-10.2 (pNi2+), and 5.2-7.0 (pZn2+). Addition of EDDS decreased free metal concentrations by a factor between 1.4 and 1.9 (Cd), 3.4-216 (Cu), 1.3-186 (Ni), and 1.3-3.3 (Zn). Model predictions of free metal concentrations were very good, and predicted values were mostly within 1 order of magnitude difference from the measured concentrations. A multicomponent approach had to be used in our model calculations, because competition between Fe and other metals for binding with EDDS was important. This was done by including the solubility of metal oxides in our model calculations. Multicomponent models can be used in chelant-assisted phytoextraction experiments to predict the speciation of dissolved metals and to increase the understanding of metal uptake by plants.     

FLAVOUR AND HAZE STABILITY DIFFERENCES DUE TO HOP TANNINS IN ALL-MALT PILSNER BEERS BREWED WITH PROANTHOCYANIDIN-FREE MALT

All-malt Pilsner beers were brewed with proanthocyanidin-free malt (ant 13 × 13 × Rupal). Hopping was with n-hexane tannin-free hop extract with or without n-hexane extracted hop residue or with whole leaf hops. The different beers were analysed chemically and presented to an expert panel to detect possible preferences and differences in bitterness and astringency. The impact of hop proantho-cyanidins on haze formation is comparable to that of malt proanthocyanidins. No differences between the beers were found in triangular tests. Statistical analysis of the paired comparison tests showed that hop proanthocyanidins do not contribute to the bitterness of beer since beer brewed with tannin-free hop extract is slightly more bitter than beer brewed with whole leaf hops. No differences in astringency were noted between beers brewed with or without hop proanthocyanidins and it was found that the panel expressed a very slight preference for beer brewed with n-hexane hop extract over beer brewed with both n-hexane hop extract and extracted hop residue.