Influence of ionic strength and pH on the limitation of latex microsphere deposition sites on iron-oxide coated sand by humic acid

This study, for the first time, investigates and quantifies the influence of slight changes in solution pH and ionic strength (IS) on colloidal microsphere deposition site coverage by Suwannee River Humic Acid (SRHA) in a column matrix packed with saturated iron-oxide coated sand.Triple pulse experimental (TPE) results show adsorbed SRHA enhances microsphere mobility more at higher pH and lower IS and covers more sites than at higher IS and lower pH. Random sequential adsorption (RSA) modelling of experimental data suggests 1 μg of adsorbed SRHA occupied 9.28 ± 0.03 × 10⁹ sites at pH7.6 and IS of 1.6 mMol but covered 2.75 ± 0.2 × 10⁹ sites at pH6.3 and IS of 20 mMol. Experimental responses are suspected to arise from molecular conformation changes whereby SRHA extends more at higher pH and lower ionic strength but is more compact at lower pH and higher IS. Results suggest effects of pH and IS on regulating SRHA conformation were additive.     

Nitrogen concentrations in mosses indicate the spatial distribution of atmospheric nitrogen deposition in Europe

In 2005/6, nearly 3000 moss samples from (semi-)natural location across 16 European countries were collected for nitrogen analysis. The lowest total nitrogen concentrations in mosses (<0.8%) were observed in northern Finland and northern UK. The highest concentrations (≥1.6%) were found in parts of Belgium, France, Germany, Slovakia, Slovenia and Bulgaria. The asymptotic relationship between the nitrogen concentrations in mosses and EMEP modelled nitrogen deposition (averaged per 50 km × 50 km grid) across Europe showed less scatter when there were at least five moss sampling sites per grid. Factors potentially contributing to the scatter are discussed. In Switzerland, a strong (r² = 0.91) linear relationship was found between the total nitrogen concentration in mosses and measured site-specific bulk nitrogen deposition rates. The total nitrogen concentrations in mosses complement deposition measurements, helping to identify areas in Europe at risk from high nitrogen deposition at a high spatial resolution.     

Vertical emission profiles for Europe based on plume rise calculations

The vertical allocation of emissions has a major impact on results of Chemistry Transport Models. However, in Europe it is still common to use fixed vertical profiles based on rough estimates to determine the emission height of point sources. This publication introduces a set of new vertical profiles for the use in chemistry transport modeling that were created from hourly gridded emissions calculated by the SMOKE for Europe emission model. SMOKE uses plume rise calculations to determine effective emission heights. Out of more than 40 000 different vertical emission profiles 73 have been chosen by means of hierarchical cluster analysis. These profiles show large differences to those currently used in many emission models. Emissions from combustion processes are released in much lower altitudes while those from production processes are allocated to higher altitudes. The profiles have a high temporal and spatial variability which is not represented by currently used profiles.     

Trace element concentrations from lichen transplants in Pretoria,South Africa

Purpose  

The purpose of this study was to assess the level and possible sources of trace elements in Tshwane metropolis using transplanted lichen thallus of Parmelia sulcata with a view to evaluating the ability of this lichen species to monitor air pollutants from a perceived polluted environment.     

Sources,distribution, and acidity of sulfate–ammonium aerosol in the Arctic in winter–spring

We use GEOS-Chem chemical transport model simulations of sulfate–ammonium aerosol data from the NASA ARCTAS and NOAA ARCPAC aircraft campaigns in the North American Arctic in April 2008, together with longer-term data from surface sites, to better understand aerosol sources in the Arctic in winter–spring and the implications for aerosol acidity. Arctic pollution is dominated by transport from mid-latitudes, and we test the relevant ammonia and sulfur dioxide emission inventories in the model by comparison with wet deposition flux data over the source continents. We find that a complicated mix of natural and anthropogenic sources with different vertical signatures is responsible for sulfate concentrations in the Arctic. East Asian pollution influence is weak in winter but becomes important in spring through transport in the free troposphere. European influence is important at all altitudes but never dominant. West Asia (non-Arctic Russia and Kazakhstan) is the largest contributor to Arctic sulfate in surface air in winter, reflecting a southward extension of the Arctic front over that region. Ammonium in Arctic spring mostly originates from anthropogenic sources in East Asia and Europe, with added contribution from boreal fires, resulting in a more neutralized aerosol in the free troposphere than at the surface. The ARCTAS and ARCPAC data indicate a median aerosol neutralization fraction [NH₄⁺]/(2[SO₄^2?] + [NO₃^?]) of 0.5 mol mol^?1 below 2 km and 0.7 mol mol^?1 above. We find that East Asian and European aerosol transported to the Arctic is mostly neutralized, whereas West Asian and North American aerosol is highly acidic. Growth of sulfur emissions in West Asia may be responsible for the observed increase in aerosol acidity at Barrow over the past decade. As global sulfur emissions decline over the next decades, increasing aerosol neutralization in the Arctic is expected, potentially accelerating Arctic warming through indirect radiative forcing and feedbacks.     

Anammox: an option for ammonium removal in bioreactor landfills

Experiments carried out in bioreactor landfill simulators demonstrated that more than 40% of the total N was transferred into the liquid and gas phases during the incubation period of 380 days. Ammonium, an end product of protein degradation and important parameter to consider during landfill closure, tends to accumulate up to inhibitory levels in the leachate of landfills especially in landfills with leachate recirculation. Most efforts to remove ammonium from leachate have been focused on ex situ and partial in situ methods such as nitrification, denitrification and chemical precipitation. Besides minimal contributions from other N-removal processes, Anammox (Anaerobic Ammonium Oxidation) bacteria were found to be active within the simulators. Anammox is considered to be an important contributor to remove N from the solid matrix. However, it was unclear how the necessary nitrite for Anammox metabolism was produced. Moreover, little is known about the nature of residual nitrogen in the waste mass and possible mechanisms to remove it. Intrusion of small quantities of O₂ is not only beneficial for the degradation process of municipal solid waste (MSW) in bioreactor landfills but also significant for the development of the Anammox bacteria that contributed to the removal of ammonium. Volatilisation and Anammox activity were the main N removal mechanisms in these pilot-scale simulators. The results of these experiments bring new insights on the behaviour, evolution and fate of nitrogen from solid waste and present the first evidence of the existence of Anammox activity in bioreactor landfill simulators.     

Influence of alumina coating on characteristics and effects of SiO2 nanoparticles in algal growth inhibition assays at various pH and organic matter contents

Silica nanoparticles (NPs) belong to the industrially most important NP types. In a previous study it was shown that amorphous SiO(2) NPs of 12.5 and 27.0 nm are stable in algal growth inhibition assays and that their ecotoxic effects are related to NP surface area. Here, it was hypothesized and demonstrated that an alumina coating completely alters the particle-particle, particle-test medium and particle-algae interactions of SiO(2) NPs. Therefore, stability and surface characteristics, dissolution, nutrient adsorption and effects on algal growth rate of both alumina coated SiO(2) NPs and bare SiO(2) NPs in OECD algal test medium as a function of pH (6.0-8.6) and natural organic matter (NOM) contents (0-12 mg C/l) were investigated. Alumina coated SiO(2) NPs aggregated in all media and adsorbed phosphate depending on pH and NOM concentration. On the other hand, no aggregation or nutrient adsorption was observed for the bare SiO(2) NPs. Due to their positive surface charge, alumina coated SiO(2) NPs agglomerated with Pseudokirchneriella subcapitata. Consequently, algal cell density measurements based on cell counts were unreliable and hence fluorescent detection of extracted chlorophyll was the preferred method. Alumina coated SiO(2) NPs showed lower toxicity than bare SiO(2) NPs at concentrations ≥46 mg/l, except at pH 6.0. At low concentrations, no clear pH effect was observed for alumina coated SiO(2) NPs, while at higher concentrations phosphate deficiency could have contributed to the higher toxicity of those particles at pH 6.0-6.8 compared to higher pH values. Bare SiO(2) NPs were not toxic at pH 6.0 up to 220 mg/l. Addition of NOM decreased toxicity of both particles. For SiO(2) NPs the 48 h 20% effect concentration of 21.8 mg/l increased 2.6-21 fold and a linear relationship was observed between NOM concentration and effective concentrations. No effect was observed for alumina coated SiO(2) NPs in presence of NOM up to 1000 mg/l. All experiments point out that the alumina coating completely altered NP interactions. Due to the difference in surface composition the SiO(2) NPs, which had the smallest surface area, were more toxic to the alga than the alumina coated SiO(2) NPs. Hence, surface modification can dominate the effect of surface area on toxicity.     

Changes in mineralogical and leaching properties of converter steel slag resulting from accelerated carbonation at low CO2 pressure

Steel slag can be applied as substitute for natural aggregates in construction applications. The material imposes a high pH (typically 12.5) and low redox potential (Eh), which may lead to environmental problems in specific application scenarios. The aim of this study is to investigate the potential of accelerated steel slag carbonation, at relatively low pCO₂ pressure (0.2 bar), to improve the environmental pH and the leaching properties of steel slag, with specific focus on the leaching of vanadium. Carbonation experiments are performed in laboratory columns with steel slag under water-saturated and -unsaturated conditions and temperatures between 5 and 90 °C. Two types of steel slag are tested; free lime containing (K3) slag and K1 slag with a very low free lime content. The fresh and carbonated slag samples are investigated using a combination of leaching experiments, geochemical modelling of leaching mechanisms and microscopic/mineralogical analysis, in order to identify the major processes that control the slag pH and resulting V leaching. The major changes in the amount of sequestered CO₂ and the resulting pH reduction occurred within 24 h, the free lime containing slag (K3-slag) being more prone to carbonation than the slag with lower free lime content (K1-slag). While carbonation at these conditions was found to occur predominantly at the surface of the slag grains, the formation of cracks was observed in carbonated K3 slag, suggesting that free lime in the interior of slag grains had also reacted. The pH of the K3 slag (originally pH ± 12.5) was reduced by about 1.5 units, while the K1 slag showed a smaller decrease in pH from about 11.7 to 11.1. However, the pH reduction after carbonation of the K3 slag was observed to lead to an increased V-leaching. Vanadium leaching from the K1 slag resulted in levels above the limit values of the Dutch Soil Quality Decree, for both the untreated and carbonated slag. V-leaching from the carbonated K3 slag remained below these limit values at the relatively high pH that remained after carbonation. The V-bearing di-Ca silicate (C2S) phase has been identified as the major source of the V-leaching. It is shown that the dissolution of this mineral is limited in fresh steel slag, but strongly enhanced by carbonation, which causes the observed enhanced release of V from the K3 slag. The obtained insights in the mineral transformation reactions and their effect on pH and V-leaching provide guidance for further improvement of an accelerated carbonation technology.     

Determination of lindane leachability in soil-biosolid systems and its bioavailability in wheat plants

The leachability of lindane from different biosolid amended soils was determined and compared to its bioavailability. Sand, soil, and a mixture of soil-sand (1:1 w/w) were spiked with lindane, blended with different amounts of biosolids, and subjected to a leaching process with water that lasted for 1-28 d. This procedure is in accordance with ISO/TS 21268-1: 2007. After these batch tests, lindane was extracted from the leachates using three different solvent-free microextraction techniques, including solid phase microextraction (SPME), stir-bar sorptive extraction (SBSE), and silicone rod extraction (SRE). The amount of lindane was determined with thermal desorption and gas chromatography coupled to mass spectrometry (GC-MS). The efficiencies of the three microextraction techniques were statistically different, and the efficiency could be related to the amount of polydimethylsiloxane (PDMS) in each extraction device. However, all of the techniques provide data that shows that the leachability of lindane is dependent on the amount of organic matter contained in the matrix.The results of the lindane leachability assay were compared to the bioavailability of lindane, which was determined by measuring the amount of lindane that accumulated in the roots of wheat plants grown in similar soil-biosolid systems.It was confirmed that the amount of organic matter in the matrix is a determining factor for lindane immobilization. The presence of biosolids decreases the mobility of lindane in all of the systems under study. Similarly, increasing biosolid concentrations in the soil significantly decreased the bioavailability of lindane and, consequently, plant absorption.The good correlation (R² = 0.997) between the leachability of lindane from the matrix and plant absorption of lindane indicates that the proposed biomimetic methodology can predict the bioavailability of lindane in a time period as short as 7 d.The results of this work confirm that amending contaminated soils with biosolids is beneficial for immobilizing lindane and helps prevent the percolation of lindane through the soil profile and into groundwater.