Removal of some elements from washed and cooked rice studied by inductively coupled plasma mass spectrometry and synchrotron based confocal micro-X-ray fluorescence

Extraction of As, Cd, Cu, Mn, Ni and Ti from two white as well as from one brown rice samples was studied by inductively coupled plasma sector field mass spectrometry (ICP-SF-MS). Samples were subjected to cold and hot water extraction (rice mass to deionised water volume ratio = 1:6, and 1:3, respectively). The discarded liquids were freeze-dried and digested by microwave-assisted digestion. About 50% of the content of the investigated elements could be extracted from the white rice. In case of the brown rice, the boiling water contained As, Cd, Ni and Ti in significant percentages. Elemental distributions in the rice grains determined by synchrotron radiation confocal micro-X-ray fluorescence analysis revealed that a surface layer having a thickness of about 80 μm is the richest region in elements. Ti was detectable only in this so-called skin region. Good correlation was observed for the extraction of As, Mn, Ni and Ti by the above-mentioned two techniques. Thus, in regions affected by heavy metal and other toxic element contamination, those rice dishes would be preferred whose preparation should need abundant amounts of water for washing and cooking, which later should be discarded.     

In vitro model improves the prediction of soil arsenic bioavailability: worst-case scenario

There is a strong interest in developing an in vitro arsenic (As) model that satisfactorily estimates the variability in in vivo relative oral bioavailability (RBA) measurements. Several in vitro tests have been developed, but none is universally accepted due to their limited success in predicting soil As RBA. A suite of amorphous and crystalline solid As phases were chosen, utilizing a worst-case scenario (WCS) that simulated fasting children's gastric solution chemistry. The objectives of this study were to (i) determine the effects of residence time, pH, and solid-to-solution ratio on As bioaccessibility and speciation in the in vitro gastric test; (ii) provide the fundamental basis for an optimized in vitro model constrained by the WCS; and (iii) validate the optimized in vitro test with the in vivo RBA obtained with BALB/c mice. The gastric pH was the only significant (p < 0.05) factor influencing solid As bioaccessibility. Bioaccessible As retained the oxidation state after its release from the solid into the gastric solution. The optimized in vitro model adequately predicted RBA values for a suite of solid As phases typically encountered in soils, with the exception of aluminum-based solids. This study is an excellent starting point for developing an in vitro test applicable to different As-contaminated soils.     

Short-term toxicological evaluation of Terminalia catappa, Pentaclethra macrophylla and Calophyllum inophyllum seed oils in rats

The purpose of this study was to evaluate the toxicological effects of feeding the oils of Calophyllum inophyllum, Pentaclethra macrophylla and Terminalia catappa to rats. The effects on physical appearance, feed intake, weight gain, plasma and tissue cholesterol and triacyglycerol levels in rats with 5% of the oils in normal rat feed were determined. Weekly monitoring of the rats showed good physical appearance and steady weight gain, with no mortality recorded for the period of the study. Haematological analysis of the rats indicated that they were not anaemic. Histopathotogical examination of the sections of the heart, liver, kidney and spleen revealed moderate (T. catappa oil) to severe fatty change and necrosis in the liver. Glomerulonephrotic changes in the kidneys of rats fed with T. catappa oil were moderate, while it was severe in the group fed with P. macrophylla oil. Severe myocardiac necrosis as well as atherosclerotic clefts in vasa vasori was observed in the vasa vasori of the hearts of rats fed with P. macrophylla oil. This change was moderate in the heart of rats fed with C. inophyllum, while no such observation was made in the group fed with T. catappa oil. There was a significant difference in the plasma cholesterol levels of the rats fed with C. inophyllum and T. catappa oils when compared with the control rats, while those fed with P. macrophylla oil had no significant difference. The oil of T. catappa appears more suitable for consumption than the oils from C. inophyllum and P. macrophylla. Fatty acid analysis of the oils showed that they have high amounts of unsaturated fatty acids with linoleic and oleic acids as the major ones.     

NMR Study of Adsorbate Self-Diffusion in Porous Glasses

The NMR pulsed field gradient technique was used to study molecular transport in porous glasses. The adsorbent materials were produced by leaching phase-separated sodium-boron-silica glasses of different composition, then heat-treating. The pore diameters of the glass samples produced were within the interval 0.8 to 50 nm. Water, methanol, dodecane, and do-decene were used as adsorbates. The coefficients of adsorbate self-diffusion were found to decrease with decreasing pore diameter. In comparison with the neat liquids, a reduction in the adsorbate mobility (up to two orders of magnitude) was observed. For the larger pores, that decrease may be attributed to the tortuosity of the adsorbent, whereas the low diffusivities in the porous glasses with small pores are a consequence of the stabilizing effect of the rigid adsorbent framework.     

Phenol and catechol biodegradation by the haloalkaliphile Halomonas campisalis: influence of pH and salinity

Removal of aromatic compounds from alkaline and/or saline industrial wastewater is an environmental concern for industry. In addition, aromatics may be accumulating in soda lakes, unique natural systems, where the fate and toxicity of these contaminants is unknown. To determine the feasibility of aromatic compound biodegradation in saline and alkaline conditions, the effect of pH and salinity on the biodegradation of phenol as a model aromatic waste compound by the haloalkaliphilic bacterium Halomonas campisalis was examined. Phenol was degraded as a source of carbon and energy at pH 8-11 and 0-150 g/L NaCl. Metabolic intermediates catechol, cis,cis-muconate, and (+)-muconolactone were identified, thus indicating that phenol was degraded via the beta-ketoadipate metabolic pathway. Although phenol and catechol were completely degraded in all cases, small amounts of cis,cis-muconate accumulated proportionally to increases in pH. There was no noticeable influence of salinity on cis,cis-muconate accumulation except at 0 g/L NaCl where it was completely degraded. These results indicate that it may be feasible to use haloalkaliphiles forthe treatment of aromatics present in saline and/or alkaline systems. This is the first report of phenol and catechol biodegradation under combined saline and alkaline conditions.     

Tribromopyrrole,brominated acids,and other disinfection byproducts produced by disinfection of drinking water rich in bromide

Using gas chromatography/mass spectrometry (GC/MS), we investigated the formation of disinfection byproducts (DBPs) from high bromide waters (2 mg/L) treated with chlorine or chlorine dioxide used in combination with chlorine and chloramines. This study represents the first comprehensive investigation of DBPs formed by chlorine dioxide under high bromide conditions. Drinking water from full-scale treatment plants in Israel was studied, along with source water (Sea of Galilee) treated under carefully controlled laboratory conditions. Select DBPs (trihalomethanes, haloacetic acids, aldehydes, chlorite, chlorate, and bromate) were quantified. Many of the DBPs identified have not been previously reported, and several of the identifications were confirmed through the analysis of authentic standards. Elevated bromide levels in the source water caused a significant shift in speciation to bromine-containing DBPs; bromoform and dibromoacetic acid were the dominant DBPs observed, with very few chlorine-containing compounds found. Iodo-trihalomethanes were also identified, as well as a number of new brominated carboxylic acids and 2,3,5-tribromopyrrole, which represents the first time a halogenated pyrrole has been reported as a DBP. Most of the bromine-containing DBPs were formed during pre-chlorination at the initial reservoir, and were not formed by chlorine dioxide itself. An exception wasthe iodo-THMs, which appeared to be formed by a combination of chlorine dioxide with chloramines or chlorine (either added deliberately or as an impurity in the chlorine dioxide). A separate laboratory study was also conducted to quantitatively determine the contribution of fulvic acids and humic acids (from isolated natural organic matter in the Sea of Galilee) as precursor material to several of the DBPs identified. Results showed that fulvic acid plays a greater role in the formation of THMs, haloacetic acids, and aldehydes, but 2,3,5-tribromopyrrole was produced primarily from humic acid. Because this was the first time a halopyrrole has been identified as a DBP, 2,3,5-tribromopyrrole was tested for mammalian cell cytotoxicity and genotoxicity. In comparison to other DBPs, 2,3,5-tribromopyrrole was 8x, 4.5x, and 16x more cytotoxic than dibromoacetic acid, 3-chloro-4-(dichloromethyl)-5-hydroxy-2-[5H]-furanone [MX], and potassium bromate, respectively. 2,3,5-Tribromopyrrole also induced acute genomic damage, with a genotoxic potency (299 microM) similar to that of MX.     

Analysis of phenolic compounds in cork from Quercus suber L. by HPLC–DAD/ESI–MS

The aim of the present work was to identify the extractable phenolic compounds present in cork from Quercus suber L. The structures of thirty three compounds were tentatively identified by liquid chromatography coupled to electrospray ionisation mass spectrometry (HPLC–DAD/ESI–MS). The majority of those compounds were gallic acid derivatives, in the form of either galloyl esters of glucose (gallotannins), combinations of galloyl and hexahydroxydiphenoyl esters of glucose (ellagitannins), dehydrated tergallic-C-glucosides or ellagic acid derivatives. Others were found to correspond to low molecular weight phenolic compounds, like acids and aldehydes. Mongolicain, a flavanoellagitannin in which hydrolysable tannin and flavan-3-ol moieties are connected through a carbon–carbon linkage, was also detected in cork from Q. suber L. The results illustrate the rich array of phenolic compounds present in cork.     

Long-term recovery of PCB-contaminated sediments at the Lake Hartwell superfund site: PCB dechlorination. 1. End-member characterization

Under anaerobic conditions, such as those typically found in buried sediments, the primary metabolic pathway for polychlorinated biphenyls (PCBs) is reductive dechlorination in which chlorine removal and substitution with hydrogen by bacteria result in a reduced organic compound with fewer chlorines. Vertical sediment cores were collected from Lake Hartwell (Pickens County, SC) and analyzed in 5-cm intervals for 107 PCB congeners in a total of more than 280 samples from 18 sediment cores and surface samples. This paper reports on extensive PCB dechlorination measured in Lake Hartwell sediments and the characterization of dechlorination end-member (EM) patterns using chemical forensic methods. PCB congener fingerprinting and a multivariate receptor modeling method, polytopic vector analysis (PVA), were used for identification and characterization of weathered and dechlorinated PCB congener patterns. Dechlorination resulted in a substantial shift in buried sediments from tetra- through decachlorobiphenyl congeners to mono- through trichlorobiphenyl congeners. Mono- through trichlorobiphenyls comprised approximately 80% of the PCBs in buried sediments that underwent maximum dechlorination as compared to approximately 20% in surface sediments. The major concentration decreases were seen in the tetra- through hexachlorobiphenyl homologues, which accounted for over 90% of the dechlorination. Octa- through decachlorobiphenyl congeners also were dechlorinated, but their overall contribution to dechlorination was relatively small due to their low initial concentrations (< 5%). The net accumulation of 2-CB, 2,2'/2,6-DCBs, 2,4'-DCB, 2,2',4-TCB, and 2,2',6-TCB at Lake Hartwell matched characteristic PCB dechlorination products reported in the literature, such as those for Processes M, Q, and C; and the persistence of tetrachlorobiphenyls (TeCBs) that contained 24- and 25-congener groups resembled dechlorination Processes H or H'. Although dechlorination tended to be very extensive in most of the cores, it was not always consistent from core to core or at various depth intervals within a single core. The reason for this variability in dechlorination extent could not be determined from the existing data and did not appear to correlate with such factors as PCB concentration, total organic carbon, or age. The authors used fingerprinting analysis and a PVA multivariate receptor model as exploratory data analysis tools to characterize PCB sources and their alteration patterns. Dominant sources and alteration patterns were determined in this large data set by comparing PVA EM patterns with known source patterns (i.e., Aroclors or Aroclor mixtures) and literature-reported alteration patterns. PVA also afforded an opportunity to characterize the vertical and lateral distributions of the weathered and unweathered PCB source patterns and dechlorination patterns, a task that would have been much more difficult to accomplish through comparison of chromatograms alone.