Two different waste-derived by-products were examined and compared. Based on the thermogravimetric tests performed, it was proved that their decomposition occurs in two weight loss steps represented by two shoulders in the derivative thermogravimetric curves. The first shoulder is attributed to the devolatilisation of hemicellulose, cellulose and lignin and the second one to the plastic fraction of the waste. Similarities in the degradation behaviour were observed for both wastes, despite of their different origin. Increased plastic fractions resulted in slightly higher conversions and lower pyrolysis rates. Enhanced lignocellulosic fractions led to higher rates during combustion. The lignocellulosic fraction was increased proportionally to the inorganic residue that remained after combustion. A wide variation of weight losses was attained even in refuse-derived fuel (RDF) samples of the same origin, whilst stronger deviations were observed in the decomposition of the plastic fraction. The independent parallel, first-order, reactions model was elaborated for the kinetic analysis of the pyrolysis results. The thermal degradation of the RDF samples was modelled assuming four parallel reactions corresponding to the devolatilisation of cellulose, hemicellulose, lignin and plastics. Increased activation energies were calculated for the plastics fraction, whilst lignin presented the lowest contribution in the pyrolysis of the samples. Generally, both RDF samples presented similar kinetic constants despite their heterogeneity.

The relation among the mean slope angle of a watershed, the stream water quality, and the chemical composition of the plagioclase component of granite was examined for 17 watersheds located in the southern part of the Northern Japan Alps in central Japan. The 17 watersheds were mainly composed of the granite. The ionic composition of the stream water can be classified into two patterns: the Ca-HCO₃-type and the Ca·Na-HCO₃-type. In all the watersheds, Na⁺ and Ca²⁺ occur in the groundwater that flows into the stream mainly due to the kaolinization of plagioclase. As compared to the watersheds with Ca-HCO₃-type stream water, the Na⁺/Ca²⁺ ratio for stream water in watersheds with Ca·Na-HCO₃-type stream water was closer to that for plagioclase in granite. This implies that the groundwater flowing in the Ca·Na-HCO₃-type watersheds is deeper than that in the Ca-HCO₃-type watersheds. The mean slope angle of Ca·Na-HCO₃-type watersheds was less acute as compared to that of Ca-HCO₃-type watersheds. The mean slope angle of the watersheds is negatively correlated with the Na⁺/Ca²⁺ ratio for stream water (r = -0.78, P <= 0.001). It is suggested that the groundwater quality at greater depths, which is comparable with the Na/Ca ratio of plagioclase, contributes more to the stream water quality in the gently sloping watersheds than in the steep watersheds. This study clarified that there is a close relation between the mean slope angle of watersheds and the depth of groundwater discharged to the stream. Moreover, it is believed that the relationship between the mean slope angle of watersheds and the Na⁺/Ca²⁺ ratio for stream water is an effective and simple index for understanding the relative depth of groundwater.

As part of the Rain In Cumulus over the Ocean Experiment (RICO) and the Puerto Rico Aerosol and Cloud Study (PRACS), cloud water was collected at East Peak (EP) in Puerto Rico. The main objective of this study was to determine the concentrations of water-soluble species (Cl⁻, NO₃ ⁻, SO₄ ²⁻, NH₄ ⁺, Ca²⁺, H⁺, Mg²⁺, K⁺, and Na⁺) in water samples taken from clouds influenced by tropical trade winds. The most abundant inorganic species were Na⁺ (average 465 μeq l⁻¹) and Cl⁻ (434 μeq l⁻¹), followed by Mg²⁺ (105 μeq l⁻¹), SO₄ ²⁻ (61 μeq l⁻¹), and NO₃ ⁻ (25 μeq l⁻¹). High concentrations of nss-SO₄ ² (28 μeq l⁻¹), NO₃ ⁻ (86 μeq l⁻¹), and H⁺ (14.5 μeq l⁻¹) were measured with a shift in air masses origin from the North Atlantic to North American continent, which reflected a strong anthropogenic influence on cloud chemistry at EP. Long-range transport of particles and acid gases seems to be the factor responsible for fluctuations in concentrations and pH of cloud water at East Peak. When under trade wind influences the liquid phase concentrations of all inorganic substances were similar to those found in clouds in other clean maritime environments.

Risk assessment of trace-metal contamination in soils requires predictive models that take into account the interaction of metal ions with other cations (e.g., H⁺ and Ca²⁺) that can change the speciation of trace metals in solution and compete for binding sites on plant roots thus affecting metal uptake and toxicity. Acid-base titrations were used to estimate the types and quantity of cation-binding sites on fresh pea (Pisum sativum L. cv. Lincoln) roots and their binding strength with protons. The roots were found to have three types of cation-binding sites with site densities of 190, 382, and 347 μmolc g⁻¹ (dry weight), respectively. The binding strength with H⁺ was indicated by the equilibrium formation constants (K HLj ). The logK HLj values under different ionic strengths were determined. At zero ionic strength, the logK HLj values are estimated to be 2.5, 5.5, and 8.3, respectively. Complementary experiments were used to validate the titration results. These included an ion exchange experiment, an experiment with HCl extractions, and a KOH neutralization method. Estimates from all four methods were consistent under the experimental conditions. The quantification of the binding capacity and the characteristics of these binding sites will assist in the development of more appropriate solution speciation models that incorporate biotic ligands. The derived parameters will provide the basis on which further development of a biotic ligand model is dependent.

The purpose of this study is to evaluate the combined Cr(VI) removal capacities of nonliving (untreated rubber wood sawdust, URWS) and living biomass (URWS-immobilized Acinetobacter haemolyticus) in a continuous laboratory scale downward-flow two column system. Synthetic solutions of Cr(VI) between 237 and 320 mg L⁻¹ were mixed with 1 g L⁻¹ brown sugar in a nonsterile condition. Final Cr(VI) of between 0 and 1.6 mg L⁻¹ indicate a Cr(VI) removal capacity of 99.8-100%. The bacterial Cr(VI) reduction capacity increased with column length. This study shows the feasibility of using the two column system consisting of living (bacteria) and nonliving biomass (URWS) as a useful alternative treatment for Cr(VI) contamination in the aqueous system.

Gypsum-rich coatings found on buildings constructed with granitic rock ashlars have been studied, from both an urban and a rural area of the NW of Spain. Previous works have attributed gypsum to rock weathering by atmospheric pollution. Mineralogical, chemical, and physical data of coatings have allowed us to distinguish six different types of coatings formed in several ways. In most cases, they are originated by the deterioration calcium-rich plaster building materials. Sulfation of Ca-rich coatings, in situ gypsum dissolution and precipitation, and deposition of air pollution particles are the most important agents related to genesis of coatings. In fact, remains of plasters practically intact were found in some studied buildings. Also, data from coatings and rock ashlars suggest that gypsum-rich coatings are not formed by environment-rock interaction. Coatings located on different parts and façades of the buildings and submitted to different environmental conditions decay in a different way.

We report observations of primary and secondary atmospheric pollutants such as nitrogen oxides, sulfur dioxide, toluene, and ozone during the period February 2002 to August 2003 in Puertollano, an industrial area located in central-southern Spain. The measurements were performed using a commercial differential optical absorption spectroscopy instrument. From the hourly data, we have analyzed the mean seasonal levels and the daily evolution and we have examined the occurrence of elevated pollution episodes. The daily cycles of NO, NO₂, SO₂, and toluene were characterized by an early-morning maximum whereas O₃ peaks were monitored around noon. Seasonally, the highest hourly mean concentrations of NO, NO₂, SO₂, and toluene, 14.2, 27.0, 34.4, and 12.1 μg m⁻³ respectively, were found in the winter while O₃ summer levels reached 119.1 μg m⁻³. The dataset presented here shows episodic occurrences of elevated concentrations that exceeded the maximum levels established in the European Directives. For instance, hourly values for SO₂ were repeatedly measured above 350 μg m⁻³. During the period of measurements, the O₃ thresholds (i.e., hourly value of 240 μg m⁻³) defined to protect the human health have also been exceeded numerous times. Finally, we investigate daily and seasonal patterns in pollution levels within the context of local meteorology and photochemistry, vehicular traffic, and industrial emissions.

Soil samples from agricultural and adjacent forest soils in Northwest Ohio were collected and analyzed for As, Cr, Cu, Ni, Pb, and Zn. pH, Eh, electrical conductivity, and moisture content were also measured. Selected samples were also evaluated for grain size and X-rayed to identify clay minerals. In this region, soils contain a large proportion of fines (~32% clay and ~37% silt) with illite, dickite, and chlorite as the main clay minerals. Surface soils in the arable land are slightly acidic (pH ~5.6) while forest soils are near-neutral to slightly basic. All soils become more basic with depth. Soil Eh and electrical conductivity range from 300 to 450 mV and 100 to 375 μS, respectively. In the soil profiles, between 0 and 50 cm depth, As increases from 4.6 to 11 mg/kg, Cr increases from19 to 23 mg/kg and Ni increases 21 to 29 mg/kg. In contrast, Cu decreases from 23 to 17 mg/kg and Pb decreases from17 to 10 mg/kg. Surface enrichment of Cu and Pb can be the result of aerosol deposition, while the downward increase in As, Cr and Ni is related to pedogenic variation. The average concentration of Zn in the samples is 64 mg/kg and does not change with land-use or depth. With the exception of As, the concentration of metals in the agricultural soil is not significantly different from the concentration in forest soil. The concentration of As in the near-surface arable soil (5.6 mg/kg) is significantly different from the concentration of As in the near-surface forest soil (4.3 mg/kg). In both cases, deeper soils have similar As contents. The relative enrichment of As in the surface arable soil could indicate input from herbicides or pesticides. The upward increase in electrical conductivity is interpreted to show that the exchangeable fraction of each metal is higher in the surface soils. However, the near neutral pH and organic, clay-rich soils may limit the mobility. The concentration of these heavy metals and As in the soils are much lower than the limits set by the United States Environmental Protection Agency.

Silicon presents a close relationship with the amelioration of heavy metals phytotoxicity. However, mechanisms of Si-mediated alleviation of metal stress remains poorly understood. This work aimed at studying the relationship between the accumulation of Si, Cd, and Zn and the tolerance and structural alterations displayed by maize plants grown on a Cd and Zn enriched soil treated with doses of Si (0, 50, 100, 150, and 200mg kg⁻¹) as calcium silicate (CaSiO₃). The results showed that the maize plants treated with Si presented not only biomass increasing but also higher metal accumulation. Significant structural alterations on xylem diameter, mesophyll and epidermis thickness, and transversal area occupied by collenchyma and midvein were also observed as a result of Si application. The deposition of silica in the endodermis and pericycle of roots seems to play an important role on the maize tolerance to Cd and Zn stress.

Laboratory culture experiments were conducted with common reed (Phragmites australis) to elucidate the role of root exudates on CH₄ production in wetland soils as well as the importance of different plant organs as routes of CH₄ to the atmosphere. In the 50 d experiment period, root exudates ranged from 0.03 to 1.53 μmolg⁻¹d⁻¹, which increased with reed growth. CH₄ production rate of soil was stimulated as root exudates collected was added. CH₄ transport capacity rate also increased with plant growth and influenced by light intensity. Root tips were the most important part of controlling diffusion of CH₄ into reed shoots, and leave transport accounted for 45.34% of total emissions into the atmosphere.