Reference conditions for rivers of the German Baltic Sea catchment: reconstructing nutrient regimes using the model MONERIS

We introduce an approach for establishing reference conditions (RC) for rivers of the German Baltic Sea catchment, based on predictive modelling. An extensive data set of statistics from the year 1880 was coupled with literature data, providing a comprehensive basis for the calculation of regional historical nutrient emissions into rivers, river nutrient concentrations, and nutrient loading into the sea. Four different scenarios were calculated: scenario 1 assumed RC following previously established criteria for lakes (Poikane et al. in Environ Manag 45(6):1286–1298, 2010), scenario 4 applied the nutrient emission conditions of 1880 (considering non-intensive land usage, the presence of tile drainage systems, sewer systems, and the human population from 1880), and scenarios 2 and 3 considered intermediate conditions. Our results showed that nutrient emissions from scenario 1 accounted for approximately one-tenth of the currently observed total nitrogen (TN) and total phosphorus (TP) emissions. The nutrient emissions calculated for 1880 (scenario 4) were found to be 47 % (TN) and 55 % (TP) higher than those calculated considering reference lake conditions (scenario 1). Our results suggest that RC nutrient concentrations in rivers in the German Baltic Sea catchment were clearly below 0.05 mg/l for TP and 1 mg/l for TN. This range is in accordance with historical and calculated pristine nutrient concentrations from other rivers in similar catchments.     

Temporal Variations of PM2.5, PM10, and Gaseous Precursors during the 1995 Integrated Monitoring Study in Central California

ABSTRACT

The spatial and temporal distributions of particle mass and its chemical constituents are essential for understanding the source-receptor relationships as well as the chemical, physical, and meteorological processes that result in elevated particulate concentrations in California’s San Joaquin Valley (SJV). Fine particulate matter ₍PM_2.5), coarse particulate matter (PM₁₀), and aerosol precursor gases were sampled on a 3-hr time base at two urban (Bakersfield and Fresno) and two non-urban (Kern Wildlife Refuge and Chowchilla) core sites in the SJV during the winter of 1995–1996.

Day-to-day variations of PM_2.5 and PM₁₀ and their chemical constituents were influenced by the synoptic-scale meteorology and were coherent among the four core sites. Under non-rainy conditions, similar diurnal variations of PM_2.5 and coarse aerosol were found at the two urban sites, with concentrations peaking during the nighttime hours. Conversely, PM_2.5 and coarse aerosol peaked during the morning and afternoon hours at the two non-urban sites. Under rainy and foggy conditions, these diurnal patterns were absent or greatly suppressed.

In the urban areas, elevated concentrations of primary pollutants (e.g., organic and elemental carbons) during the late afternoon and nighttime hours reflected the impact from residential wood combustion and motor vehicle exhaust. During the daytime, these concentrations decreased as the mixed layer deepened. Increases of secondary nitrate and sulfate concentrations were found during the daylight hours as a result of photochemical reactions. At the non-urban sites, the same increases in secondary aerosol concentrations occurred during the daylight hours but with a discernable lag time. Concentrations of the primary pollutants also increased at the non-urban sites during the daytime. These observations are attributed to mixing aloft of primary aerosols and secondary precursor gases in urban areas followed by rapid transport aloft to non-urban areas coupled with photochemical conversion.     

PM2.5 source apportionment: reconciling receptor models for U.S. nonurban and urban long-term networks

Chemical mass balance (CMB) and trajectory receptor models were applied to speciated particulate matter with aerodynamic diameter < or =2.5 microm (PM2.5) measurements from Speciation Trends Network (STN; part of the Chemical Speciation Network [CSN]) and Interagency Monitoring of Protected Visual Environments (IMPROVE) monitoring network across the state of Minnesota as part of the Minnesota PM2.5 Source Apportionment Study (MPSAS). CMB equations were solved by the Unmix, positive matrix factorization (PMF), and effective variance (EV) methods, giving collective source contribution and uncertainty estimates. Geological source profiles developed from local dust materials were either incorporated into the EV-CMB model or used to verify factors derived from Unmix and PMF. Common sources include soil dust, calcium (Ca)-rich dust, diesel and gasoline vehicle exhausts, biomass burning, secondary sulfate, and secondary nitrate. Secondary sulfate and nitrate aerosols dominate PM2.5 mass (50-69%). Mobile sources outweigh area sources at urban sites, and vice versa at rural sites due to traffic emissions. Gasoline and diesel contributions can be separated using data from the STN, despite significant uncertainties. Major differences between MPSAS and earlier studies on similar environments appear to be the type and magnitude of stationary sources, but these sources are generally minor (<7%) in this and other studies. Ensemble back-trajectory analysis shows that the lower Midwestern states are the predominant source region for secondary ammoniated sulfate in Minnesota. It also suggests substantial contributions of biomass burning and soil dust from out-of-state on occasions, although a quantitative separation of local and regional contributions was not achieved in the current study. Supplemental materials are available for this article. Go to the publisher's online edition of the Journal of the Air & Waste Management Association for a summary of input data, Unmix and PMF factor profiles, and additional maps.     

Application of a computational model for Michael addition reactivity in the prediction of toxicity to Tetrahymena pyriformis

A computational model to predict acute aquatic toxicity to the ciliate Tetrahymena pyriformis has been developed. A general prediction of toxicity can be based on three consecutive steps: 1. Identification of a potential reactive mechanism via structural alerts; 2. Confirmation and quantification of (bio)chemical reactivity; 3. Establishing a relationship between calculated reactivity and toxicity. The method described herein uses a combination of a reactive toxicity (RT) model, including computed kinetic rate constants for adduct formation (log k) via a Michael acceptor mechanism of action, and baseline toxicity (BT), modelled by hydrophobicity (octanol-water partition coefficient). The maximum of the RT and BT values defines acute toxicity for a particular compound. The reactive toxicity model is based on site-specific steric and quantum chemical ground state electronic properties. The performance of the model was examined in terms of predicting the toxicity of 106 potential Michael acceptor compounds covering several classes of compounds (aldehydes, ketones, esters, heterocycles). The advantages of the computational method are described. The method allows for a closer and more transparent mechanistic insight into the molecular initiating events of toxicological endpoints.     

Hydrogen production by catalytic aqueous-phase reforming of waste biomass: a review

Environmental Chemistry Letters - The rising adverse effects of climate change call for a rapid shift to low-carbon energy and reducing our dependence on fossil fuels. For that, biorefineries...     

Placental transfer of polychlorinated biphenyls, their hydroxylated metabolites and pentachlorophenol in pregnant women from eastern Slovakia

The aim of the present study was to understand the placental transfer of polychlorinated biphenyls (PCBs), specific hydroxylated PCB metabolites (OH-PCBs), and pentachlorophenol (PCP) in blood serum, in a birth cohort from eastern Slovakia. During the period 2002-2004, cord blood specimens were collected in parallel with maternal specimens from women delivering in the two eastern Slovak districts of Michalovce and Svidnik/Stropkov. A total of 92 pairs of mother-cord specimens at delivery were selected for this study. 4-OH-CB107, 3-OH-CB153, 4-OH-CB146, 3'-OH-CB138, 4-OH-CB187, and 4'-OH-CB172 were quantified. The median concentrations of Sigma(17)PCBs, Sigma(6)OH-PCBs, and PCP in cord serum were 0.92, 0.33, and 0.69 ng/g wet wt., respectively and highly correlated with the corresponding maternal serum levels (correlations were R(2)=0.61, 0.78, and 0.82, respectively). The median cord to mother ratios of the Sigma(17)PCBs, Sigma(6)OH-PCBs, and PCP were 0.18, 0.75, and 1.10, respectively. The median ratio of the Sigma(6)OH-PCBs to the Sigma(17) PCBs in the cord serum was 0.38 from wet weight based concentrations, which was about four times higher than the ratio of these compounds in maternal serum (0.09). PCP was more abundant than any PCB or OH-PCB congener measured in cord serum. The higher cord to maternal ratios of OH-PCB metabolites as compared with the parent compounds suggests either a higher placental transfer rate or greater metabolism in the fetus as compared with the maternal compartment. These findings are consistent with their preferential binding to TTR that can cross the placenta. The cord to maternal ratio varies by congener (e.g., 4-OH-CB107=0.58, 4-OH-CB146=0.74, 3'-OH-CB138=1.01).     

Microcosm investigations of stormwater pond sediment toxicity to embryonic and larval amphibians: variation in sensitivity among species

Stormwater ponds have become common features of modern development and often represent significant amounts of open space in urbanized areas. Although stormwater ponds may provide habitat for wildlife, factors responsible for producing variation in wildlife use of ponds have received limited attention. To investigate the role of variation in species tolerances of pollutants in structuring pond-breeding amphibian assemblages, we exposed species tolerant (Bufo americanus) and not tolerant (Rana sylvatica) of urbanization to pond sediments in laboratory microcosms. Pond microcosms had elevated sediment metal levels and chloride water concentrations. Among R. sylvatica embryos, exposure to pond sediments resulted in 100% mortality. In contrast, B. americanus embryos and larvae experienced only sublethal effects (i.e., reduced size at metamorphosis) due to pond sediment exposure. Our results suggest variation in pollutant tolerance among early developmental stages of amphibians may act in concert with terrestrial habitat availability to structure amphibian assemblages associated with stormwater ponds.     

Source apportionment: findings from the U.S. Supersites Program

Receptor models are used to identify and quantify source contributions to particulate matter and volatile organic compounds based on measurements of many chemical components at receptor sites. These components are selected based on their consistent appearance in some source types and their absence in others. UNMIX, positive matrix factorization (PMF), and effective variance are different solutions to the chemical mass balance (CMB) receptor model equations and are implemented on available software. In their more general form, the CMB equations allow spatial, temporal, transport, and particle size profiles to be combined with chemical source profiles for improved source resolution. Although UNMIX and PMF do not use source profiles explicitly as input data, they still require measured profiles to justify their derived source factors. The U.S. Supersites Program provided advanced datasets to apply these CMB solutions in different urban areas. Still lacking are better characterization of source emissions, new methods to estimate profile changes between source and receptor, and systematic sensitivity tests of deviations from receptor model assumptions.     

Dissolution and transport of TNT, RDX, and composition B in saturated soil columns

Low-order detonations and blow-in-place procedures on military training ranges can result in residual solid explosive formulations to serve as distributed point sources for ground water contamination. This study was conducted to determine if distribution coefficients from batch studies and transport parameters of pure compounds in solution adequately describe explosive transport where compounds are present as solid particles in formulations. Saturated column transport experiments were conducted with 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and the explosive formulation, Composition B (Comp B) (59.5 +/- 2.0% RDX, 39.5 +/- 2.3% TNT, and 1% wax) in solid and dissolved forms. The two soils used were Plymouth loamy sand (mesic, coated Typic Quartzipsamments) from Camp Edwards, MA and Adler silt loam (coarse-silty, mixed, superactive, thermic Fluvaquentic Eutrudepts) from Vicksburg, MS. Interrupted flow experiments were used to determine if explosives were at equilibrium distribution between soil and solution phases. The HYDRUS-1D code was used to determine fate and transport parameters. Results indicated that sorption of high explosives was rate limited. The behavior of dissolved Comp B was similar to the behavior of pure TNT and RDX. Behavior of solid Comp B was controlled by dissolution that depended on physical properties of the Comp B sample. Adsorption coefficients determined by HYDRUS-1D were different from those determined in batch tests for the same soils. Use of parameters specific to formulations will improve fate and transport predictions.