Investigation of uranium binding forms in selected German mineral waters

Cryogenic time-resolved laser-induced fluorescence spectroscopy was successfully used to identify uranium binding forms in selected German mineral waters of extremely low uranium concentrations (<2.0 μg/L). The measurements were performed at a low temperature of 153 K. The spectroscopic data showed a prevalence of aquatic species Ca₂UO₂(CO₃)₃ in all investigated waters, while other uranyl–carbonate complexes, viz, UO₂CO_3(aq) and UO₂(CO₃)₂ ^2?, only existed as minor species. The pH value, alkalinity (CO₃ ^2?), and the main water inorganic constituents, specifically the Ca²⁺ concentration, showed a clear influence on uranium speciation. Speciation modeling was performed using the most recent thermodynamic data for aqueous complexes of uranium. The modeling results for the main uranium binding form in the investigated waters indicated a good agreement with the spectroscopy measurements.     

Investigation of MSWI fly ash melting characteristic by DSC-DTA

The melting process of MSWI (Municipal Solid Waste Incineration) fly ash has been studied by high-temperature DSC-DTA experiments. The experiments were performed at a temperature range of 20-1450 degrees C, and the considerable variables included atmosphere (O(2) and N(2)), heating rates (5 degrees C/min, 10 degrees C/min, 20 degrees C/min) and CaO addition. Three main transitions were observed during the melting process of fly ash: dehydration, polymorphic transition and fusion, occurring in the temperature range of 100-200 degrees C, 480-670 degrees C and 1101-1244 degrees C, respectively. The apparent heat capacity and heat requirement for melting of MSWI fly ash were obtained by DSC (Differential Scanning Calorimeter). A thermodynamic modeling to predict the heat requirements for melting process has been presented, and it agrees well with the experimental data. Finally, a zero-order kinetic model of fly ash melting transition was established. The apparent activation energy of MSWI fly ash melting transition was obtained.     

Polychlorinated biphenyl, polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran residues in sediments and fish of the River Nile in the Cairo region

The levels of organohalogenated contaminants, i.e. PCBs, PCDDs and PCDFs were determined in sediment and fish samples collected from different locations in the River Nile, Egypt. Thirty-six sediment and eighteen fish samples were carried out during a period of 12 months from February 2003 to February 2004. Determination of PCBs and dioxins was carried out using a high resolution GC mass spectrometer. The results indicated that the PCB and PCDD/F mean concentrations in sediment samples ranged from 1461 to 2244 and from 240 to 775pgg(-1) dry wt basis, respectively. The mean concentration of PCBs and PCDD/Fs in fish samples were found to be in the range from 695 to 853pgg(-1) fresh wt for PCB congeners and from 27.7 to 121pgg(-1) lipid for total PCDD/Fs. Moreover, the concentrations of both PCBs and PCDD/Fs were found to be different at different locations along the River Nile. It could be concluded that the contamination of the River Nile is within the permissible limits set by the FDA and the Egyptian Standards for fish and shellfish.     

In vitro biotransformation of surfactants in fish. Part I: linear alkylbenzene sulfonate (C12-LAS) and alcohol ethoxylate (C13EO8)

Developing regulatory activities (e.g., REACh, [DGEE. 2003. Directorates General Enterprise and Environment. The new EU chemicals legislation REACH. DG Enterprise, Brussels, Belgium. (http://www.europa.eu.int/comm/enterprise/reach/index_en.htm)]) will require bioaccumulation to be assessed for thousands of chemicals. Further, there is increasing pressure to reduce, refine or replace animal tests. Given this scenario, there is an urgent need to evaluate the feasibility of in vitro systems to supply data useful for bioaccumulation estimation. Subcellular and cellular hepatic systems were tested to determine the biotransformation of two surfactants: C12-2-LAS (2-phenyl dodecane p-sulfonate) and an alcohol ethoxylate C13EO8 (Octaethylene glycol monotridecyl ether). The subcellular systems tested were liver homogenates and microsomes from the common carp (Cyprinus carpio) and rainbow trout (Oncorhynchus mykiss). Cellular systems consisted of primary hepatocytes from the common carp (Cyprinus carpio) and PLHC-1 cells, hepatocarcinoma cells from the desert topminnow (Poeciliopsis lucida). All in vitro systems were exposed to radiolabeled test compounds and assayed for biotransformation using liquid scintillation and thin layer chromatographic methods. First-order kinetics were used to estimate rates of biotransformation. Bioconcentration of test materials in fish were predicted using an in vitro to in vivo metabolic rate extrapolation model linked to a mass-balance model commonly used to predict bioaccumulation in fish. Subcellular biotransformation rates for each of the surfactants were greatest with microsomes. Cellular loss rates exceeded subcellular rates, leading to lower predicted BCF values. Predicted BCFs corresponded closely to measured values in several fish species, verifying the utility of in vitro systems in refining Kow-only-based BCFs via the inclusion of biotransformation rates.     

Speciation and toxicological relevance of manganese in humans

Although manganese is an essential trace element, concerns are rising about the Mn exposure of humans being related to neurotoxic effects. This review summarizes several aspects of this topic to provide updated information on Mn related investigations, including chemical speciation of Mn-compounds. The paper starts with some chemical aspects of Mn and its compounds, enlightening oxidation states in general and in biological matrices. This is followed by considerations on natural sources of human exposure, on occupational sources and on anthropogenically caused environmental sources, for example from the use of methylcyclopentadienyl manganese tricarbonyl (MMT). Next, the paper deals with Mn levels in the human organism, showing normal Mn concentrations in various tissues or body fluids, and continues with the toxicology of Mn, i.e. absorption, distribution and excretion. Of specific concern is the transfer of Mn to the brain which is the relevant neurotoxic target. In this context, parallels and differences between primary and Mn-dependent Parkinsonism are discussed, concluding with a risk assessment and a consideration of susceptible groups. The main part of this review focuses on recent investigations on Mn speciation. Analytical problems and their solutions are also described for correct identification of relevant Mn-compounds in matrices of human origin. Finally, future needs are discussed, such as further investigations on those Mn-species which may overcome neural barrier control, on disease-modulated barrier control, on susceptibility to certain Mn-species, and on the interaction of Mn with Fe-homeostasis in the brain.     

Impact of clouds and aerosols on ozone production in Southeast Texas

A radiative transfer model and photochemical box model are used to examine the effects of clouds and aerosols on actinic flux and photolysis rates, and the impacts of changes in photolysis rates on ozone production and destruction rates in a polluted urban environment like Houston, Texas. During the TexAQS-II Radical and Aerosol Measurement Project the combined cloud and aerosol effects reduced j(NO₂) photolysis frequencies by nominally 17%, while aerosols reduced j(NO₂) by 3% on six clear sky days. Reductions in actinic flux due to attenuation by clouds and aerosols correspond to reduced net ozone formation rates with a nearly one-to-one relationship. The overall reduction in the net ozone production rate due to reductions in photolysis rates by clouds and aerosols was approximately 8 ppbv h^?1.     

Heterogeneous conversion of nitric acid to nitrous acid on the surface of primary organic aerosol in an urban atmosphere

Nitrous acid (HONO), nitric acid (HNO₃), and organic aerosol were measured simultaneously atop an 18-story tower in Houston, TX during August and September of 2006. HONO and HNO₃ were measured using a mist chamber/ion chromatographic technique, and aerosol size and chemical composition were determined using an Aerodyne quadrupole aerosol mass spectrometer. Observations indicate the potential for a new HONO formation pathway: heterogeneous conversion of HNO₃ on the surface of primary organic aerosol (POA). Significant HONO production was observed, with an average of 0.97 ppbv event^?1 and a maximum increase of 2.2 ppb in 4 h. Nine identified events showed clear HNO₃ depletion and well-correlated increases in both HONO concentration and POA-dominated aerosol surface area (SA). Linear regression analysis results in correlation coefficients (r²) of 0.82 for HONO/SA and 0.92 for HONO/HNO₃. After correction for established HONO formation pathways, molar increases in excess HONO (HONO_excess) and decreases in HNO₃ were nearly balanced, with an average HONO_excess/HNO₃ value of 0.97. Deviations from this mole balance indicate that the residual HNO₃ formed aerosol-phase nitrate. Aerosol mass spectral analysis suggests that the composition of POA could influence HONO production. Several previously identified aerosol-phase PAH compounds were enriched during events, suggesting their potential importance for heterogeneous HONO formation.     

Mercury species measured atop the Moody Tower TRAMP site,Houston, Texas

Atmospheric mercury speciation was monitored within Houston, Texas, USA, August 6–October 14, 2006 as part of the TexAQS Radical and Aerosol Measurement Program (TRAMP). On average, all mercury levels were significantly elevated compared to a rural Gulf of Mexico coastal site. Concentrations varied from very clean to very dirty. Multi-day periods of stagnant or low-wind conditions brought elevated concentrations of all mercury species, whereas multi-day periods of strong winds, particularly southerly winds off the Gulf of Mexico, brought very low values of mercury species. Over the entire mercury measurement period, the daily averages of mercury species showed distinct and consistent relationships with the average planetary boundary layer dynamics, with gaseous elemental and particulate-bound mercury near-surface concentrations enhanced by a shallow nocturnal boundary layer, and reactive gaseous mercury concentration enhanced by midday convective boundary layer air entrainment transporting air aloft to the surface. Mercury concentrations were not significantly correlated with known products of combustion, likely indicating non-combustion mercury sources from the Houston area petrochemical complexes. On the morning of August 31, 2006 an observed emission event at a refinery complex on the Houston Ship Channel resulted in extremely high concentrations of aerosol mass and particulate-bound mercury at the TRAMP measurement site 20 km downwind.     

VOC source–receptor relationships in Houston during TexAQS-II

During the TRAMP field campaign in August–September 2006, C₂–C₁₀ volatile organic compounds (VOCs) were measured continuously and online at the urban Moody Tower (MT) site. This dataset was compared to corresponding VOC data sets obtained at six sites located in the highly industrialized Houston Ship Channel area (HSC). Receptor modeling was performed by positive matrix factorization (PMF) at all sites. Conditional probability functions (CPF) were used to determine the origin of the polluted air masses in the Houston area. A subdivision into daytime and nighttime was carried out to discriminate photochemical influences. Eight main source categories of industrial, mobile, and biogenic emissions were identified at the urban receptor site, seven and six, respectively, at the different HSC sites. At MT natural gas/crude oil contributed most to the VOC mass (27.4%), followed by liquefied petroleum gas (16.7%), vehicular exhaust (15.3%), fuel evaporation (14.3%), and aromatics (13.4%). Also petrochemical sources from ethylene (4.7%) and propylene (3.6%) play an important role. A minor fraction of the VOC mass can be attributed to biogenic sources mainly from isoprene (4.4%). Based on PMF analyses of different wind sectors, the total VOC mass was estimated to be twofold at MT with wind directions from HSC compared to air from a typical urban sector, for petrochemical compounds more than threefold. Despite the strong impact of air masses influenced by industrial sources at HSC, still about a third of the total mass contributions at MT can be apportioned to other sources, mainly motor vehicles and aromatic solvents. The investigation of diurnal variation in combination with wind directional frequencies revealed the greatest HSC impact at the urban site during the morning, and the least during the evening.