UN/ECE ICP Materials Dose-response Functions for the Multi-pollutant Situation

A “multi-pollutant exposure programme” reflecting the new pollution situation where SO₂ is no longer the dominating pollutant has been performed by the International Co-operative Programme on Effects on Materials, including Historic and Cultural Monuments (ICP Materials) within the activities of the Convention on Long-range Transboundary Air Pollution. The main results obtained in the period 1997–2003 are summarised. Dose-response functions are presented for carbon steel, zinc, copper, bronze and limestone. Parameters involved in the functions include besides SO₂ and pH, which were included in the previously developed functions from ICP Materials, also the effect of particulate matter and HNO₃.     

Effect of unburned carbon on lead, zinc, and copper recovery from molten fly ash by chloride-induced volatilization

The present work focuses on investigation of the effective recovery of heavy metals from molten fly ash by applying chloride-induced volatilization. In particular, the effect of unburned carbon on the chloride-induced volatilization of lead, zinc, and copper from model and real molten fly ashes was investigated in the temperature range 873–1173 K under a N₂ atmosphere. As a result, almost 100% of lead and a significant proportion of zinc were volatilized from the real molten fly ash samples at 1173 K. In contrast, for the model fly ash, volatilization ratios of lead and zinc at 1173 K were only 85% and 25%, respectively. Further, the results of X-ray diffraction analysis suggested that PbO in molten fly ash was converted either to Pb₂OCl₂ or Pb by respective chlorination and reduction reactions. Meanwhile ZnO and CuO in the molten fly ash were reduced to Zn and Cu by reaction with unburned carbon. Subsequently, Pb, Zn, and Pb₂OCl₂ were volatilized, but Cu remained in the solid residue. Finally, the volatilization ratio of zinc increased with the addition of carbon, and more than 98% of zinc was volatilized at 1173 K from a fly ash with a carbon content of 20%.     

Resurrection of the iron and phosphorus resource in steel-making slag

 This research focused on the treatment of steel-making slags to recycle and recover iron and phosphorus. The carbothermal reduction behavior of both synthesized and factory steel-making slag in microwave irradiation was investigated. The slags were mixed with graphite powder and heated to a temperature higher than 1873 K to precipitate a lump of Fe–C alloy with a diameter of 2–8 mm. The larger the carbon equivalent (C_eq, defined in the text), the higher the fractional reduction of iron and phosphorus. An increase in the SiO₂ content of slag led to a considerable improvement in the reduction for both iron and phosphorus because of the improvement in the fluidity of the slags and an increase in the activity coefficient of P₂O₅ in the slags. The extraction behavior of phosphorus from Fe–P–C_satd alloy was also investigated at 1473 K by carbonate flux treatment. For all the experiments with a processing time longer than 10 min, the phosphorus in the fluxes could be concentrated to more than 9% (w/w) showing that it could be used as a phosphorus resource. Compared with K₂CO₃ flux treatment, that using Na₂CO₃ was more effective for the extraction of phosphorus, and this was attributed to the lower evaporation of Na₂CO₃. Finally, a recycling scheme for steel-making slag is proposed. Received: March 16, 2001 / Accepted: November 12, 2001     

Assessing Aerobic Biodegradability of Plastics in Aqueous Environment by GC-Analyzing Composition of Equilibrium Gaseous Phase

Testing biodegradability of plastics under varied conditions of the environment as well as under laboratory conditions in accordance with valid international standards is very laborious, lengthy and often also economically demanding. For this reason, applicability was verified of gas chromatography to analyze gaseous phase when investigating the biodegradation course of plastics in an aqueous environment as an alternative to customary employed methods. A mathematical model of acid–basic CO₂ equilibrium in a gas–liquid system was worked out, enabling to determine quantity of produced CO₂ through chromatographic analysis of gaseous phase, in dependence on ratio of liquid and gas phase volumes (V _l/V _g) and on actual pH of liquid phase. Experimental conditions for organizing the tests were optimized. A ratio that proved suitable was V _l/V _g ≅ 0.1 at pH ≈ 7.1 of liquid phase. Under these test conditions, biodegradability of model samples, PHB, Gellan gum and Xanthan gum, was explored; course of biodegradation was studied through produced CO₂ (values ) determined by analyzing gaseous phase through gas chromatography on the one hand, and through customary “titration” procedure on the other. With water-soluble polymers, the decrement in dissolved organic carbon (values D _DOC) was also studied. Difference between values does not exceed 5%. The procedures in question are alternative “substituting” procedures for observing course of aerobic biodegradation of substances in an aqueous environment.     

Pyrrolidinium Imides: Promising Ionic Liquids for Direct Capture of Elemental Mercury from Flue Gas

A new approach to vapor phase elemental mercury capture has been explored; this approach exploits an ionic liquid coating layer to oxidize elemental mercury for subsequent immobilization by chelating ligands. The room temperature ionic liquid 1-butyl-1-methyl pyrrolidinium bis(trifluoromethane sulfonyl)imide (P₁₄) was selected for study based on its oxidation potential window, thermal stability, and low vapor pressure. Tests were also completed in which KMnO₄ was added to P₁₄ to form a new ionic liquid, P₁₄–KMnO₄, with a higher oxidation potential. In room-temperature bulk liquid phase capture experiments, 59% of the elemental mercury in the inlet gas was captured using P₁₄ alone; mercury capture using P₁₄–KMnO₄ was quantitative. P₁₄ and P₁₄–KMnO₄ coatings were successfully applied to mesoporous silica substrates and to silica substrates functionalized with mercury chelating ligands. The coating layers were found to be thermally stable up to 300°C. Fixed-bed tests of nonfunctionalized silica coated with P₁₄ showed an elemental mercury uptake of 2.7 mg/g adsorbent at 160°C; at the same temperature, functionalized silica coated with P₁₄–KMnO₄ showed an elemental mercury capacity of at least 7.2 mg/g adsorbent, several times higher than that of activated carbon. The empty bed gas residence time in these tests was 0.04 s. A chelating adsorbent incorporating P₁₄ in the coating layer, may be capable of simultaneous removal of elemental and oxidized mercury from coal combustion flue gases.     

PM<Subscript>10</Subscript> and Ultrafine Particles Counts In-Vehicle and On-Road in the Athens Area

This work presents the first results of a study concerning on-road and in-vehicle exposure to particulate matter in the area of Athens. PM₁₀ concentration measurements were conducted by TSI DustTrak, while driving along routes with different characteristics of traffic density, during September 2003–March 2004. Concurrent measurements of the ultrafine particles (UFPs) number concentration were also conducted, by condensation particle counter during part of the days. Pedestrian exposure to PM₁₀ and UFPs was also studied through stationary measurements on the kerbside of selected roads on November 2003 and February 2004. A major avenue, a heavy-trafficked road across a children hospital and two central roads, one in a residential and one in a commercial area were selected for measurement. The results indicate that every day commuters are exposed to significant concentration levels. Higher exposures were observed in heavy-trafficked areas and during rush hours. Mean PM₁₀ in-vehicle and on-road concentrations ranged from 30–320 μg/m³ and 70–285 μg/m³, respectively. The ultrafine particles number concentrations were in the range of 5.0 × 10⁴–17.3 × 10⁴ particles/cm³ in-vehicle and 3.1 × 10⁴–7.3 × 10⁴ particles/cm³ on the kerbside of a central residential road. Both PM₁₀ and UFPs concentrations presented repeated short-term peak exposures. The results clearly point out the importance of the road microenvironment (in-vehicle and on kerbside) for population exposure in urban areas.     

Fate and behavior of metal(loid) contaminants in an organic matter-rich shooting range soil: Implications for remediation

This study investigates the fate and behavior of lead (Pb), copper (Cu), antimony (Sb), and arsenic (As) in a shooting range soil. The soil samples were collected from the surface (0–15 cm) and the subsurface (15–40 cm and 40–55 cm) of a grassy and wood chip covered impact area behind a firing position. Optical microscopy images indicate significant amounts of corroded bullet fragments and organic wood chips in the surface soil. Analysis by X-ray powder diffraction (XRPD) and scanning electron microscopy electron dispersive X-ray spectroscopy (SEM-EDS) showed that metallic Pb was transformed into lead oxides (litharge PbO and massicot PbO) and lead carbonates (hydrocerussite Pb₃(CO₃)₂(OH)₂, cerussite PbCO₃, and plumbonacrite Pb₅(CO₃)₃O(OH)₂). Rietveld quantification indicated the surface soil contained 14.1% metallic Pb, 17.9% hydrocerussite, 5.2% plumbonacrite, 5.9% litharge, and 3.9% massicot on a dry weight basis, or a total of 39.7% Pb, far in excess of lead concentrations typically found in US shooting range soils. Metallic Cu (bullet jacket material) appeared stable as no secondary minerals were detected in the surface soil. As and Sb concentrations were on the order of 1,057 mg/kg and 845 mg/kg respectively. The elevated soil pH coupled with high organic carbon content is thought to have caused downward migration of metals, especially for Pb, since 4,153 mg Pb/kg was observed at a depth of 55 cm. More than 60% of Pb was concentrated in the coarse soil (> 0.425 mm) fraction, suggesting soil clean-up possible by physical soil washing may be viable. The concentrations of Pb, As, and Sb in the toxicity characteristic leaching procedure (TCLP) extracts were 8,869 mg/L, 6.72 mg/L, and 6.42 mg/L respectively, were above the USEPA non-hazardous regulatory limit (As and Pb) of 5 mg/L. The elevated Sb and As concentrations draw concern because there is historically limited information concerning these metals at firing ranges and several values exceeded local soil cleanup criteria. As the high Pb concentrations appeared to be linked to the presence of organic-rich berm cover materials, the use of wood chips as berm cover to prevent soil erosion requires reconsideration as a shooting range management practice.     

Effect of additives on dechlorination of PVC by mechanochemical treatment

Polyvinyl chloride (–CH₂–CHCl–) _n (PVC) was ground with a powdered inorganic material (CaO, CaCO₃, SiO₂, Al₂O₃, or slag) in a planetary ball mill under atmospheric conditions to investigate the effect of additions on its dechlorination. The grinding causes a dehydrochlorinating reaction, forming a mixture of partially dechlorinated PVC and inorganic chloride, depending on the grinding time. The dechlorination increases as the grinding progresses, and is improved with increasing amounts of additives. The most effective additive is a mixture of CaO, SiO₂, and Al₂O₃, which has the same constituent components as blast furnace slag. CaO, a mixture of CaO, SiO₂, and blast furnace slag, are also effective, but CaCO₃ is the least effective additive tired. Received: August 3, 2000 / Accepted: September 21, 2000     

Ozone Deposition to a Coniferous and Deciduous Forest in the Czech Republic

Estimates of ozone concentration and deposition flux to coniferous and deciduous forest in the Czech Republic on a 1 × 1 km grid during growing season (April–September) of the year 2001 are presented. Ozone deposition flux was derived from ozone concentrations in the atmosphere and from its deposition velocities. To quantify the spatial pattern in surface concentrations at 1 km resolution incorporating topography, empirical methods are used. The procedure maps ozone concentrations from the period of the day when measurements are representative for the forest areas of countryside. The effects of boundary layer stability are quantified using the observed relationship between the diurnal variability of surface ozone concentration and altitude. Ozone deposition velocities were calculated according to a multiple resistance model incorporating aerodynamic resistance (R _a ), laminar layer resistance (R _b ) and surface resistance (R _c ). Surface resistance (R _c ) comprises stomatal resistance (R _sto ). R _sto was calculated with respect to global radiation, surface air temperature and land cover. Modelled total and stomatal ozone fluxes are compared with the maps describing equivalent values of AOT40 (accumulated exposure over threshold of 40 ppb). For forests, the critical level (9,000 ppbh May–July daylight hours) is exceeded over 50% of forested territory. This indicates the potential for effects on large areas of forest. There is significiant correspondence between the exposure index AOT40 and the total ozone flux, but the relation between the total ozone flux and AOT40 exposure index is not clear in all parts of the forest territory.     

Production and characterization of KOH-activated carbon derived from polychlorinated biphenyl residue generated by the sodium dispersion process

Polychlorinated biphenyl (PCB) residues from the sodium dispersion (SD) process were employed as the raw materials for the production of activated carbon using KOH activation. The pore properties, such as the specific surface area and pore size distribution, were characterized using the Barrett–Joyner–Halenda method and the Horvath–Kawazoe method based on the N₂ adsorption isotherm at 77 K. The activated carbon produced showed similar adsorption capacities and specific surface areas to the commercially available product. The effects of the activation conditions on the porosity of the activated carbon produced were studied. The most significant factor affecting the specific surface proved to be the activation temperature. The activated carbon produced from PCB residues from the high-temperature (423–443 K) SD process had a binary pore size distribution well developed in the 4 nm region and in the micropore region. The pore structure of the carbon produced from PCB residues from the low-temperature (333–393 K) SD process had a wide range of micropores and mesopores.     

Trends in Chemical Composition of Wet-only Precipitation at Rural French Monitoring Stations Over the 1990–2003 Period

The long-term monitoring of precipitation and its chemical composition are important for identifying trends in rain quality and for assessing the effectiveness of pollution control strategies. A statistical test has been used to the atmospheric concentrations measured in the French rural monitoring network (MERA) in order to bring out spatio-temporal trends in precipitation quality in France over the period 1990–2003. The non-parametric Mann–Kendall test which has been developed for detecting and estimating monotonic trends in the time series was used and applied in our study at annual values of wet-only precipitation concentrations. The emission data suggest that SO₂ and NO _x emissions decreased (−3.3 and −2.0% year⁻¹, respectively) contrary to NH₃ emissions that increased slightly (+0.2% year⁻¹) over the period 1990–2002 in France. On the national scale, the pH values have a significant decreasing trend of −0.025 ± 0.02 unit pH year⁻¹. and concentrations in precipitation have a significant decreasing trend, −3.0 ± 1.6 and −3.3 ± 0.6% year⁻¹, respectively, corresponding with the downward trends in SO₂ emissions in France (−3.3% year⁻¹). A good correlation (R ² = 0.84) between SO₂ emissions and concentrations was obtained. The decreasing trend of was more significant (−5.4 ± 5.2% year⁻¹) than that of (−1.3 ± 2.4% year⁻¹). Globally, the concentration of the major ions showed a clear downward trend including marine and alkaline ions. In addition, the relative contribution of HNO₃ to acidity precipitation increased by 51% over the studied period.     

Natural Weathering of Kenaf Bast Fibre-Filled Poly(Butylene Succinate) Composites: Effect of Fibre Loading and Compatibiliser Addition

Natural weathering was performed on poly(butylene succinate) (PBS) and its kenaf bast fibre (KBF) filled composites by exposing the specimens to a tropical climate for a period of 6 months (max–min temperature: 31.5–23.9 °C; relative humidity: 78.9%). The aim of this study was to investigate the effects of KBF loading and the addition of maleated PBS compatibiliser (PBSgMA) on the performance of the composites under natural weathering. As expected, the flexural properties of both the uncompatibilised and compatibilised composites dropped with increasing exposure time. The weathered specimens were also assessed by colour change analysis, FTIR spectroscopy analysis and SEM examination. The total colour change, ΔE _ab , of both the uncompatibilised and compatibilised composites increased with weathering time. FTIR spectroscopy analysis confirmed the presence of oxidation products such as hydroxyl, carbonyl and vinyl species in the weathered uncompatibilised and compatibilised composites. SEM examination revealed the presence of surface defects such as cracking, tiny holes and degraded fibre, which explain the poor performance of the composites upon weathering.     

Determination of nitrous oxide, methane, and ammonia emissions from a swine waste composting process

The amounts of harmful gas emissions from the process of composting swine waste were determined using an experimental composting apparatus. Forced aeration (19.2–96.1 l/m³/min) was carried out continuously, and exhaust gases were collected and analyzed periodically. With weekly turning and the addition of a bulking agent in order to decrease the moisture content and increase air permeability, the temperature of most of the contents rose to 70°C and composting was complete within 3–5 weeks. NH₃, CH₄, and N₂O emissions were high in the early stage of composting. About 10%–25% of the nitrogen in the raw material was lost as NH₃ gas during composting. The emission rate of NH₃ mainly depended on the aeration rate, so that as the aeration rate rose, the level of NH₃ emissions increased. The CH₄ and N₂O emissions could be kept lower with adequate treatment at more than 40 l/m³/min aeration. N₂O may be mainly the result of the denitrification of NO _x -N in the additional matured compost used as a composting accelerator. Received: September 11, 1998 / Accepted: November 8, 1999     

Effects of Acid Rain on Competitive Releases of Cd, Cu, and Zn from Two Natural Soils and Two Contaminated Soils in Hunan, China

Leaching experiments of rebuilt soil columns with two simulated acid rain solutions (pH 4.6–3.8) were conducted for two natural soils and two artificial contaminated soils from Hunan, south-central China, to study effects of acid rain on competitive releases of soil Cd, Cu, and Zn. Distilled water was used in comparison. The results showed that the total releases were Zn>Cu>Cd for the natural soils and Cd>Zn≫Cu for the contaminated soils, which reflected sensitivity of these metals to acid rain. Leached with different acid rain, about 26–76% of external Cd and 11–68% external Zn were released, but more than 99% of external Cu was adsorbed by the soils, and therefore Cu had a different sorption and desorption pattern from Cd and Zn. Metal releases were obviously correlated with releases of TOC in the leachates, which could be described as an exponential equation. Compared with the natural soils, acid rain not only led to changes in total metal contents, but also in metal fraction distributions in the contaminated soils. More acidified soils had a lower sorption capacity to metals, mostly related to soil properties such as pH, organic matter, soil particles, adsorbed SO₄ ²⁻, exchangeable Al³⁺ and H⁺, and contents of Fe₂O₃ and Al₂O₃.     

Identification,Abundance and Origin of Aliphatic Hydrocarbons in the Fine Atmospheric Particulate Matter of Athens,Greece

The organic chemical composition of the fine fraction of atmospheric particulate matter in Athens has been studied, in order to establish emission sources. The results of the analyses of the aliphatic fraction indicate that all samples contain n-alkanes ranging from C₁₄ to C₃₂, with C₂₅, C₂₆, C₂₇ and C₂₉ being the more abundant congeners. Fossil fuels biomarkers such as extended tricyclic terpanes (hopanes, steranes) and isoprenoid hydrocarbons (pristane, phytane) were observed in our samples on a daily basis. Source reconciliation was conducted using molecular diagnostic ratios (such as the carbon preference index – CPI). The mean CPI value (1.84) indicates the mixed origin of the Athenian fine particles. The notable presence of an unresolved complex mixture or “hump” of hydrocarbons in our gas chromatograms is indicative of petrogenic hydrocarbon inputs. An approximate measure of this kind of contamination is the ratio of the concentrations of unresolved components to the resolved n-alkanes and other major compounds (U:R). The high U:R value of 25.25 further confirmed the major contribution of fossil fuels. Yet, the percent contribution of leaf wax n-alkanes (25.15%) indicated the parallel contribution of biogenic sources. This work supports the conclusion that vehicular emissions were the major source of aliphatic organic compounds with a smaller contribution of biogenic n-alkanes during the study period in Athens.     

Polyethylene conversion by partial oxidation in supercritical water

This paper gives the results of partial oxidation experiments of polyethylene (PE) in supercritical water (SCW). The experiments were carried out at a reaction temperature of 693K and a reaction time of 30 min using 6 cm³ of a batch-type reactor. The loaded sample weight was 0.3 g and there was 2.52 g water (0.42 g/cm³). The ratio of oxygen atoms to carbon atoms was 0.3. The results show a significant CO formation in O₂–SCW, and the 1-alkene/n-alkane ratio in partial oxidation was higher than that in SCW pyrolysis. These results suggest the possibility of the hydrogenation of hydrocarbon through partial oxidation followed by a water–gas shift reaction. Received: July 19, 2000 / Accepted: September 28, 2000     

Synthesis of hydrogarnet from molten slag and its hydrogen chloride fixation performance at high temperature

Hydrogarnet was synthesized hydrothermally below 200°C using molten slag obtained from municipal solid waste. For comparison, it was also synthesized using pure-phase CaO–Al₂O₃–SiO₂–H₂O, as reported previously. The structural and textural properties of this material were investigated using various analytical and spectroscopic techniques such as X-ray diffraction, X-ray fluorescence spectrometry, atomic absorption spectrometry (AAS), thermogravimetry/differential thermal analysis, Fourier transform infrared spectroscopy, and scanning electron microscopy. The Cl⁻ fixation ability of hydrogarnet was investigated in the temperature range 500–800°C in a fixed-bed flow reactor using a HCl concentration (1000 p.p.m.v.) similar to that of incinerator exhaust gas. Under these experimental conditions, the hydrogarnet was capable of reducing the HCl gas level to less than 1 p.p.m.v. Analysis of the spent catalyst revealed that the hydrogarnet was being transformed into wadalite and CaCl₂ at high temperatures. The elution test for chromium ions in hydrogarnet obtained from slag was also used, and it was found that chromium ions were not eluted from hydrogarnet. Received: January 27, 2001 / Accepted: October 11, 2001     

Production of hydrogen by steam gasification of dehydrochlorinated poly(vinyl chloride) or activated carbon in the presence of various alkali compounds

Steam gasification of dehydrochlorinated poly(vinyl chloride) (PVC) or activated carbon was carried out in the presence of various alkali compounds at 3.0 MPa and 560°C–660°C in a batch reactor or in a semi-batch reactor with a flow of nitrogen and steam. Hydrogen and sodium carbonate were the main products, and methane and carbon dioxide were the minor products. Yields of hydrogen were high in the presence of sodium hydroxide and potassium hydroxide. The acceleration effect of the alkali compounds on the gasification reaction was as follows: KOH > NaOH > Ca(OH)₂ > Na₂CO₃. The rate of gasification increased with increasing partial steam pressure and NaOH/C molar ratio. However, the rate became saturated at a molar ratio of NaOH/C greater than 2.0.     

Release Characteristics of Nutrients from Polymer-coated Compound Controlled Release Fertilizers

Reliable information regarding release characteristics of nutrients from a polymer-coated controlled release fertilizer (CRF) is essential for beneficial agronomic and environmental results. Significant knowledge regarding nitrogen release from polymer-coated urea was gained while the information regarding the release of the different nutrients contained in polymer-coated compound N–P–K CRF remains limited. An experiment in which major factors affecting the differential release of nutrients from two coated compound CRF was performed in free water, water saturated sand and sand at field capacity. In general, nitrate release was the fastest, followed by ammonium and potassium whereas phosphate was significantly slower, with a rate of linear release in free water 45–70% slower than that of nitrate. Little differences were obtained for the lag periods of nitrate, ammonium and potassium release (2–10 days) under the experimental conditions, whereas for P they were one order of magnitude larger. The main factor slowing the release was assumed to be the lower solubility of ions with P being the least soluble. Release into free water was, expectedly, somewhat faster than that into saturated sand and significantly faster as compared to sand at field capacity and particularly so for P. Raising the temperature from 20 °C to 40 °C increased the rate of linear release of the different nutrients. The energy of activation, EA_rel, estimated for the linear release, of the different nutrients, was narrow ranging between 37 to 46 (KJ mol⁻¹) whereas the mean values obtained for the two CRF, differing by 50% in coating thickness, was non-significant. However, EA_rel was significantly different in different media. The complex effect of temperature on the lag period and nutrient interactions during release deserve further investigation.     

Decomposition of mixed plastics consisting of polypropylene and polyethylene terephthalate into oils over titania/silica catalysts

The catalytic decomposition of mixed plastics consisting of polypropylene (PP) and polyethylene terephthalate (PET) has been investigated over titania/silica catalysts at 698 K. The yield of oil produced was about 70%, and the large amounts of C₁₈₊ hydrocarbons this contained was from the aromatics in PET. Gas was also produced, including C₃–C₅ hydrocarbons. The carbon-number fractions in the oil was influenced by the PET/(PP + PET) ratios and the catalyst weight. The titania/silica catalysts could be used repeatedly, and after they had been fouled, could be regenerated. From the Fourier Transform Infrared (FT–IR) spectroscopic data of adsorbed pyridine on the catalyst surface, most of the acid sites of the titania/silica catalysts were found to be Lewis sites where the hydride abstracted from PP pyrolysates react with PET pyrolysates to form oil and gas. Received: July 19, 2000 / Accepted: October 20, 2000