Acute effects of Fe₂O₃, TiO₂, ZnO and CuO nanomaterials on Xenopus laevis

Metal oxide nanomaterials have exhibited toxicity to a variety of aquatic organisms, especially microbes and invertebrates. To date, few studies have evaluated the toxicity of metal oxide nanomaterials on aquatic vertebrates. Therefore, this study examined effects of ZnO, TiO₂, Fe₂O₃, and CuO nanomaterials (20-100 nm) on amphibians utilizing the Frog Embryo Teratogenesis Assay Xenopus (FETAX) protocol, a 96 h exposure with daily solution exchanges. Nanomaterials were dispersed in reconstituted moderately hard test medium. These exposures did not increase mortality in static renewal exposures containing up to 1000 mg L⁻¹ for TiO₂, Fe₂O₃, CuO, and ZnO, but did induce developmental abnormalities. Gastrointestinal, spinal, and other abnormalities were observed in CuO and ZnO nanomaterial exposures at concentrations as low as 3.16 mg L⁻¹ (ZnO). An EC₅₀ of 10.3 mg L⁻¹ ZnO was observed for total malformations. The minimum concentration to inhibit growth of tadpoles exposed to CuO or ZnO nanomaterials was 10 mg L⁻¹. The results indicate that select nanomaterials can negatively affect amphibians during development. Evaluation of nanomaterial exposure on vertebrate organisms are imperative to responsible production and introduction of nanomaterials in everyday products to ensure human and environmental safety.     

Effect of coal-fired power generation on visibility in a nearby national park

The Mohave coal-fired power plant has long been considered a major contributor to visibility impairment in Grand Canyon National Park. The permanent closure of the plant in 2005 provides the opportunity to test this assertion. Although this analysis, based on data from the Interagency Monitoring of Protected Environments (IMPROVE) Aerosol Network, shows that fine sulfate levels in the park dropped following the closure, no statistically significant improvement in visibility resulted. Difference-in-differences estimation was used to control for other influences. This finding has important implications for the methods generally employed to attribute visibility reductions to air pollution sources.     

Hydroxyl radical (OH) yields from the ozonolysis of both double bonds for five monoterpenes

A new method has been applied to determine OH-radical yields from the ozonolysis of both double bonds from five selected, atmospherically relevant monoterpenes, namely terpinolene, α-phellandrene, limonene, α-terpinene and γ-terpinene. While OH-yields for the faster reacting double bond agreed with previous literature values, the yields from the second double bond were determined for the first time and are as follows: limonene 7–10%, terpinolene 39–48%, α-phellandrene 8–11% and α-terpinene 12–14%. Only for γ-terpinene the rate coefficient for the reaction of ozone with the two double bonds was too similar in order to distinguish the OH-yield with this method. In all cases the yield from the second double bond was significantly lower than the first. The reasons for this difference are discussed in terms of the Criegee-intermediate reactions, in particular the number of abstractable H-atoms and the number of possible hydroperoxide products.     

Characterization of colored products formed during irradiation of aqueous solutions containing H2O2 and phenolic compounds

Irradiation of aqueous (pH = 5) mixtures containing hydrogen peroxide (1 mM) and phenolic compounds (10 mM) were found to produce visible light absorbing solutions over the course of several hours. The kinetics and products of these reactions were studied by UV–VIS absorbance, electrospray mass spectrometry, FTIR, fluorescence, and NMR and compared to humic-like substances commonly found in atmospheric particulate matter. It was determined the reactions leading to formation of color are quite general to this compound class, and the reactions proceeded more rapidly with hydroxyl or methoxy substitution ortho to the phenolic OH. However, para substitution generally slowed formation of colored compounds compared to the unsubstituted form. Mass spectrometry confirms compounds of several hundred Da formed in the reaction mixtures. The IR spectra of the reaction products bear similarity to that observed for authentic aerosol humic-like substances. The results indicate radical coupling of phenols and methoxylated phenols in tropospheric waters may contribute to humic-like particulate matter.     

A summary of the 209 PCB congener nomenclature

Primary publications of congener numbering shorthand systems for PCB congener identification were reviewed, including the original Ballschmiter-Zell (BZ) system; recommended changes by Schulte and Malisch, and Guitart et al.; and listings by the Chemical Abstracts Service. Comparisons of the various congener numbering shorthands and chlorine substitution numberings in the structural name listings are presented. Several changes, to adhere more closely to IUPAC rules, have been incorporated into the BZ structural nomenclature, and these resulted in renumbering congeners. These corrected listings have been erroneously identified as "IUPAC" numbers, a misnomer, because IUPAC has not published a shorthand system. Guitart pointed out additional inconsistencies with IUPAC rules for nine congeners which would result in further order changes, but did not recommend renumbering, to avoid further confusion. We noted an additional error in the structural name for congener 97, named 2,2',3',4,5 using Ballschmiter and Zell nomenclature and 2,2',3,4',5' using strict IUPAC nomenclature. This renaming would cause the renumbering of the IUPAC number system reported by Guitart for isomers 91 through 98. No further changes are recommended, however. Tables summarizing each publication, and the discrepancies between them are provided in hopes of clarifying the current state of the nomenclature.     

Arsenic speciation in arsenic-rich Brazilian soils from gold mining sites under anaerobic incubation

BACKGROUND: Arsenic speciation in environmental samples is essential for studying toxicity, mobility and bio-transformation of As in aquatic and terrestrial environments. Although the inorganic species As(III) and As(V) have been considered dominant in soils and sediments, organisms are able to metabolize inorganic forms of arsenic into organo-arsenic compounds. Arsenosugars and methylated As compounds can be found in terrestrial organisms, but they generally occur only as minor constituents. We investigated the dynamics of arsenic species under anaerobic conditions in soils surrounding gold mining areas from Minas Gerais State, Brazil to elucidate the arsenic biogeochemical cycle and water contamination mechanisms. METHODS: Surface soil samples were collected at those sites, namely Paracatu Formation, Banded Iron Formation and Riacho dos Machados Sequence, and incubated in CaCl2 2.5 mmol L(-1) suspensions under anaerobic conditions for 1, 28, 56 and 112 days. After that, suspensions were centrifuged and supernatants analyzed for soluble As species by IC-ICPMS and HPLC-ICPMS. RESULTS: Easily exchangeable As was mainly arsenite, except when reducible manganese was present. Arsenate was mainly responsible for the increase in soluble arsenic due to the reductive dissolution of either iron or manganese in samples from the Paracatu Formation and Riacho dos Machados Sequence. On the other hand, organic species of As dominated in samples from the Banded Iron Formation during anaerobic incubation. DISCUSSION: Results are contrary to the expectation that, in anaerobic environments, As release due to the reductive dissolution of Fe is followed by As(V) reduction to As(III). The occurrence of organo-arsenic species was also found to be significant to the dynamics of soluble arsenic, mainly in soils from the Banded Iron Formation (BIF), under our experimental conditions. CONCLUSIONS: In general, As(V) and organic As were the dominant species in solution, which is surprising under anaerobic conditions in terrestrial environments. The unexpected occurrence of organic species of As was attributed to enrollment of ternary organic complexes or living organisms such as algae or cyanobacteria. PERSPECTIVES: These findings are believed to be useful for remediation strategies in mine-affected regions, as the organic As species are in general considered to be less toxic than inorganic ones and even As(V) is considered less mobile and toxic than As(III).     

Trace metal enrichments in core sediments in Muthupet mangroves, SE coast of India: application of acid leachable technique

Core sediments from Mullipallam Creek of Muthupet mangroves on the southeast coast of India were analyzed for texture, CaCO(3), organic carbon, sulfur and acid leachable trace metals (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn and Cd). Textural analysis reveals a predominance of mud while CaCO(3) indicates dissolution in the upper half of the core, and reprecipitation of carbonates in reduction zones. Trace metals are diagenetically modified and anthropogenic processes control Pb and, to some extent, Ni, Zn and Fe. A distinct event is identified at 90 cm suggesting a change in deposition. Strong relationship of trace metals with Fe indicates that they are associated with Fe-oxyhydroxides. The role of carbonates in absorbing trace metals is evident from their positive relationship with trace metals. Comparison of acid leachable trace metals indicates increase in concentrations in the study area and the sediments act as a sink for trace metals contributed from multiple sources.     

Organohalogen contamination in breeding glaucous gulls from the Norwegian Arctic: associations with basal metabolism and circulating thyroid hormones

Exposure to organohalogens in endotherms has been suggested to impose chemically induced stress by affecting functions related to maintenance energy requirements. Effects on basal metabolic rate (BMR) have been suggested to be, in part, mediated through interactions with the thyroid hormones (THs). We investigated the relationships between plasma concentrations of major organochlorines, PBDEs, hydroxylated (OH)- and methoxylated (MeO)-PBDEs and OH-PCBs, circulating TH levels and BMR in breeding glaucous gulls (Larus hyperboreus) from the Norwegian Arctic. Negative associations were found between BMR and concentrations of sigma PCB, Sigma DDT and particularly Sigma chlordane, which combined made up 91% of the total contaminant burden. Levels of THs (thyroxine and triiodothyronine) were not associated significantly with variation of BMR or concentrations of any of the compounds determined. The present study suggests that BMR may be altered in glaucous gulls exposed to high loadings of persistent contaminants in the Norwegian Arctic environment.     

Analysis of per- and polyfluorinated alkyl substances in air samples from Northwest Europe

Air samples were collected from 4 field sites in Europe: 2 sites from the UK, Hazelrigg (semi-rural) and Manchester (urban); 1 site from Ireland: Mace Head (rural); and 1 site from Norway: Kjeller (rural). Additionally, air samples were taken from indoor locations in Troms?, Norway. Air samples were collected using high-volume air samplers employing sampling modules containing glass-fibre filters (GFFs, particle phase), and glass columns with a polyurethane foam (PUF)-XAD-2-PUF sandwich (gaseous phase). Typical outdoor air volumes required for the determination of per- and polyfluorinated alkyl substances (PFAS) ranged from 500-1800 m3. GFFs and PUF-XAD columns were analysed separately to obtain information on phase partitioning. All air samples were analysed for volatile, neutral PFAS, with selected GFF samples halved for analysis of both neutral and airborne particle-bound ionic PFAS. Volatile PFAS were extracted from air samples by cold-column immersion with ethyl acetate, and were analysed by gas chromatography-mass spectrometry in the positive chemical ionisation mode (GC-PCI-MS). Ionic PFAS were extracted from GFFs by sonication in methanol, and were analysed by liquid chromatography-time-of-flight-mass spectrometry (LC-TOF-MS) using electrospray ionisation in the negative ion mode (ESI-). Perfluorooctanoate (PFOA) was often the predominant analyte found in the particulate phase at concentrations ranging from 1-818 pg m(-3), and 8:2 fluorotelomer alcohol (FTOH) and 6:2 FTOH were the prevailing analytes found in the gas phase, at 5-243 pg m(-3) and 5-189 pg m(-3), respectively. These three PFAS were ubiquitous in air samples. Many other PFAS, both neutral and ionic, were also present, and levels of individual analytes were in the 1-125 pg m(-3) range. Levels of some PFAS exceeded those of traditional persistent organic pollutants (POPs). In this study, the presence of 12:2 FTOH and fluorotelomer olefins (FTolefins), and ionic PFAS other than perfluorooctane sulfonate (PFOS) and PFOA, are reported in air samples for the first time. Concentrations of neutral PFAS were several orders of magnitude higher in indoor air than outdoor air, making homes a likely important diffuse source of PFAS to the atmosphere. Our repeated findings of non-volatile ionic PFAS in air samples raises the possibility that they might directly undergo significant atmospheric transport on particles away from source regions, and more atmospheric measurements of ionic PFAS are strongly recommended.