Sulfate removal from waste chemicals by precipitation

Chemical oxidation using Fenton's reagent has proven to be a viable alternative to the oxidative destruction of organic pollutants in mixed waste chemicals, but the sulfate concentration in the treated liquor was still above the acceptable limits for effluent discharge. In this paper, the feasibility of sulfate removal from complex laboratory wastewaters using barium and calcium precipitation was investigated. The process was applied to different wastewater cases (two composite samples generated in different periods) in order to study the effect of the wastewater composition on the sulfate precipitation. The experiments were performed with raw and oxidized wastewater samples, and carried out according to the following steps: (1) evaluate the pH effect upon sulfate precipitation on raw wastewaters at pH range of 2-8; (2) conduct sulfate precipitation experiments on raw and oxidized wastewaters; and (3) characterize the precipitate yielded. At a concentration of 80 g L(-1), barium precipitation achieved a sulfate removal up to 61.4% while calcium precipitation provided over 99% sulfate removal in raw and oxidized wastewaters and for both samples. Calcium precipitation was chosen to be performed after Fenton's oxidation; hence this process configuration favors the production of higher quality precipitates. The results showed that, when dried at 105 degrees C, the precipitate is composed of hemidrate and anhydrous calcium sulfate ( approximately 99.8%) and trace metals ( approximately 0.2%: Fe, Cr, Mn, Co, Ag, Mg, K, Na), what makes it suitable for reuse in innumerous processes.     

Microbiological and physical–chemical water quality of the rice fields in Sinos River’s basin, Southern Brazil

In this study, we evaluate spatial and temporal variations of the water’s quality used in rice fields. Every 15 days during the different phases of cultivation of the rice—vegetative, reproductive, and maturity—samples were collected from the main irrigation channel, from the surface water in the field, and from the excess-water drainage channel. The differences in the values of 13 variables were analyzed by the analysis of variance system and by the Principal Component Analysis (PCA) technique. The results demonstrate that the values observed for the presence of total coliforms, heat-tolerant coliforms, and pH were higher in the irrigation water and that the calcium and magnesium components were greater in the drainage water. The PCA results indicate that three groups of variance exist and that these three account for 77 % of the observed variances. The first principal component, (39 % of the variances), includes the variables pH, phosphorus, potassium, carbon, and turbidity; the second (28.1 %), calcium, magnesium, and conductivity; while the third accounts for only 9.9 % of the variation and incorporates the variable biological thermotolerant coliforms. The spatial pattern resulting from the distribution of the sampling locations as regards the first two principal components indicates a difference between the irrigation and drainage waters. The variables of the first and third items (except for the turbidity in the second component) reach higher values in the irrigation water, while the variables associated with the second component have higher values in the drainage water. The information provided is important for the analysis of the influence exercised by plantation management decisions on the microbiological, physical, and chemical quality of the water. The results confirm the ability of paddy rice field to filter out some of the chemicals and coliforms from the irrigation water as it passes through the agro ecosystem.     

X-ray absorption and photoelectron spectroscopy investigation of selenite reduction by Fe-bearing minerals

The long-lived radionuclide ⁷⁹Se is one of the elements of concern for the safe storage of high-level nuclear waste, since clay minerals in engineered barriers and natural aquifer sediments strongly adsorb cationic species, but to lesser extent anions like selenate (Se^VIO₄²⁻) and selenite (Se^IVO₃²⁻). Previous investigations have demonstrated, however, that Se^IV and Se^VI are reduced by surface-associated Fe^II, thereby forming insoluble Se⁰ and Fe selenides. Here we show that the mixed Fe^II/^III (hydr)oxides green rust and magnetite, and the Fe^II sulfide mackinawite reduce selenite rapidly (< 1 day) to FeSe, while the slightly slower reduction by the Fe^II carbonate siderite produces elemental Se. In the case of mackinawite, both S^−II and Fe^II surface atoms are oxidized at a ratio of one to four by producing a defective mackinawite surface. Comparison of these spectroscopic results with thermodynamic equilibrium modeling provides evidence that the nature of reduction end product in these Fe^II systems is controlled by the concentration of HSe⁻; Se⁰ forms only at lower HSe⁻ concentrations related to slower HSeO₃⁻ reduction kinetics. Even under thermodynamically unstable conditions, the initially formed Se solid phases may remain stable for longer periods since their low solubility prevents the dissolution required for a phase transformation into more stable solids. The reduction by Fe²⁺-montmorillonite is generally much slower and restricted to a pH range, where selenite is adsorbed (pH < 7), stressing the importance of a heterogeneous, surface-enhanced electron transfer reaction. Although the solids precipitated by the redox reaction are nanocrystalline, their solubility remains below 6.3 × 10^− 8 M. No evidence for aqueous metal selenide colloids nor for Se sorption to colloidal phases was found. Since Fe^II phases like the ones investigated here should be ubiquitous in the near field of nuclear waste disposals as well as in the surrounding aquifers, mobility of the fission product ⁷⁹Se may be much lower than previously assumed.     

Uncertainty in Agricultural CH<Subscript>4</Subscript> AND N<Subscript>2</Subscript>O Emissions from Finland – Possibilities to Increase Accuracy in Emission Estimates

According to the United Nations Framework Convention on Climate Change (UNFCCC) and Kyoto Protocol under it, industrial countries have to estimate their greenhouse gas emissions annually, and assess the uncertainties in these estimates. In Finland, agricultural methane (CH₄) and nitrous oxide (N_2O) emissions represent 7% of anthropogenic greenhouse gas emissions, and globally the share is much higher. Agriculture is one of the most uncertain emission categories (representing over 20% of greenhouse gas inventory uncertainty in Finland), due to both high natural variability of the emission sources and poor knowledge of the emission-generating processes. In this paper, we present an uncertainty estimate of agricultural CH₄ and N₂O emissions from Finland in 2002. Uncertainties were estimated based on measurement data, literature and expert judgement, and total uncertainty in agriculture was calculated using Monte Carlo simulation. According to the calculations, agricultural CH₄ and N₂O emissions from Finland were 3.7 to 7.8 Tg carbon dioxide (CO₂) equivalents, 5.4 Tg being the mean value.Estimates of CH₄ emissions are more reliable than those of N₂O. N₂O from agricultural soils was the most uncertain emission category, and the uncertainty was not reduced by using available national measurement data of N₂O fluxes. Sensitivity study revealed that the uncertainty in total agricultural inventory could be 7% points lower, if more accurate emission estimation methods were used, including 1) improved data collection in area estimates of organic soils, 2) climate-specific methods for N₂O from agricultural soils as already presented in literature, and 3) more detailed CH₄ estimation methods for enteric fermentation which can be achieved by investigating national circumstances and digestible systems of animals in more detail.     

The Role of Fungal Symbioses in the Adaptation of Plants to High Stress Environments

All plants studied in natural ecosystemsare symbiotic with fungi that either resideentirely (endophytes) or partially(mycorrhizae) within plants. Thesesymbioses appear to adapt to biotic andabiotic stresses and may be responsible forthe survival of both plant hosts and fungalsymbionts in high stress habitats. Here wedescribe the role of symbiotic fungi inplant stress tolerance and present astrategy based on adaptive symbiosis topotentially mitigate the impacts of globalchange on plant communities.     

Effect of different tannery sludge compost amendment rates on growth,biomass accumulation and yield responses of Capsicum plants

Composting has been recognized as one of the most cost effective and environmentally sound alternatives for organic wastes recycling from long and composted wastes have a potential to substitute inorganic fertilizers. We investigated the potential of composted tannery sludge for ornamental purposes and to examine the effects of two different composts and concentrations on ornamental Capsicum growth. The two composts were produced with tannery sludge and the composition of each compost was: compost₁ of tannery sludge (C₁TS) – tannery sludge + sugarcane straw and cattle manure mixed in the ratio 1:3:1 (v:v:v); compost₂ of tannery sludge (C₂TS) – tannery sludge + “carnauba” straw and cattle manure in the ratio 1:3:1 (v:v:v). Each compost was amended with soil at rates (% v:v) of 0%, 25%, 50%, 75% and 100% (designation hereafter as T₁–T₅, respectively). The number of leaves and fruits were counted, and the stem length was also measured. Chlorophyll content was recorded on three leaves of each harvested plant prior to harvest. Number of leaves and fruits, stem length, dry weight of shoot and roots did not vary significantly between the plants grown in two tannery composts. All the treatments with composted tannery sludge application (T₂–T₅) significantly increased the number of leaves and fruits, stem length and chlorophyll content compared with the control (T₁). The chlorophyll content was higher in plants growing in the C₁TS compared to C₂TS. The results of the present study further suggest that Capsicum may be a good option to be grown on composted tannery amended soil.     

Chemical composition and hygroscopic properties of size-segregated aerosol particles collected at the Adriatic coast of Slovenia

The chemical composition as well as the water uptake characteristics of aerosols was determined in size-segregated samples collected during November 2002 on the Slovenian coast. Major ions, water-soluble organic compounds (WSOC), short-chain carboxylic acids and trace elements were determined in the water-soluble fraction of the aerosol. Total aerosol black carbon (BC) was measured from filter samples. Our results showed that the origin of air masses is an important factor that controls the variation in the size distribution of the main components. Very high concentrations of WSOC as well as higher concentrations of BC were found under mostly continental influence. Besides the main ionic species (SO4(2-), NH4(+), K+) in the finest size fraction (0.17-0.53 microm), the concentration of NO3(-) was also high. The difference between the two different air mass origins is particularly expressed for Cl-, Na+, Mg2+ and Ca2+ determined in particles larger than 1.6 microm. As expected, a very good correlation was found between Na+ and Cl-. A good correlation was found between sea salt elements and elements of crustal origin (Na+, Cl-, Mg2+, Ca2+, Sr). A good relationship between typical anthropogenic tracers (K, V and Pb) was also observed. The mass growth factors, for all size fractions of aerosols collected under continental influence were very low (maximum 2.23 at 94%, 1.6-5.1 microm), while under marine influence the mass growth factors increased significantly with the particle size. At 97% humidity, the mass growth factors were 6.95 for the size fraction 0.53-1.6 microm and 9.78 for larger particles (1.6-5.1 microm).     

Survey of mercury,cadmium and lead content of household batteries

The objective of this work was to provide updated information on the development of the potential impact of heavy metal containing batteries on municipal waste and battery recycling processes following transposition of the new EU Batteries Directive 2006/66/EC. A representative sample of 146 different types of commercially available dry and button cells as well as lithium-ion accumulators for mobile phones were analysed for their mercury (Hg)-, cadmium (Cd)- and lead (Pb)-contents. The methods used for preparing the cells and analysing the heavy metals Hg, Cd, and Pb were either developed during a former study or newly developed. Several batteries contained higher mass fractions of mercury or cadmium than the EU limits. Only half of the batteries with mercury and/or lead fractions above the marking thresholds were labelled. Alkaline–manganese mono-cells and Li-ion accumulators, on average, contained the lowest heavy metal concentrations, while zinc–carbon batteries, on average, contained the highest levels.