Use of thermal analysis techniques (TG-DSC) for the characterization of diverse organic municipal waste streams to predict biological stability prior to land application

The use of organic municipal wastes as soil amendments is an increasing practice that can divert significant amounts of waste from landfill, and provides a potential source of nutrients and organic matter to ameliorate degraded soils. Due to the high heterogeneity of organic municipal waste streams, it is difficult to rapidly and cost-effectively establish their suitability as soil amendments using a single method. Thermal analysis has been proposed as an evolving technique to assess the stability and composition of the organic matter present in these wastes. In this study, three different organic municipal waste streams (i.e., a municipal waste compost (MC), a composted sewage sludge (CS) and a thermally dried sewage sludge (TS)) were characterized using conventional and thermal methods. The conventional methods used to test organic matter stability included laboratory incubation with measurement of respired C, and spectroscopic methods to characterize chemical composition. Carbon mineralization was measured during a 90-day incubation, and samples before and after incubation were analyzed by chemical (elemental analysis) and spectroscopic (infrared and nuclear magnetic resonance) methods. Results were compared with those obtained by thermogravimetry (TG) and differential scanning calorimetry (DSC) techniques. Total amounts of CO₂ respired indicated that the organic matter in the TS was the least stable, while that in the CS was the most stable. This was confirmed by changes detected with the spectroscopic methods in the composition of the organic wastes due to C mineralization. Differences were especially pronounced for TS, which showed a remarkable loss of aliphatic and proteinaceous compounds during the incubation process. TG, and especially DSC analysis, clearly reflected these differences between the three organic wastes before and after the incubation. Furthermore, the calculated energy density, which represents the energy available per unit of organic matter, showed a strong correlation with cumulative respiration. Results obtained support the hypothesis of a potential link between the thermal and biological stability of the studied organic materials, and consequently the ability of thermal analysis to characterize the maturity of municipal organic wastes and composts.     

Resource limitation of bacterial production distorts the temperature dependence of oceanic carbon cycling

Our view of the effects of temperature on bacterial carbon fluxes in the ocean has been confounded by the interplay of resource availability. Using an extensive compilation of cell-specific bacterial respiration (BRi) and production (BPi), we show that both physiological rates respond to changing temperature in a similar manner and follow the predictions of the metabolic theory of ecology. Their apparently different temperature dependence under warm, oligotrophic conditions is due to strong resource limitation of BP, but not of BRi. Thus, and despite previous preconception, bacterial growth efficiency (BGE = BPi/[BPi + BRi]) is not directly regulated by temperature, but by the availability of substrates for growth. We develop simple equations that can be used for the estimation of bacterial community metabolism from temperature, chlorophyll concentration, and bacterial abundance. Since bacteria are the greatest living planktonic biomass, our results challenge current understanding of how warming and shifts in ecosystem trophic state will modify oceanic carbon cycle feedbacks to climate change.     

Construction demolition wastes, Waelz slag and MSWI bottom ash: a comparative technical analysis as material for road construction

The objective of the study is to analyze the technical suitability of using secondary materials from three waste flows (construction and demolition waste (CDW), Waelz slag and municipal solid waste incineration (MSWI) bottom ash), under the regulations and standards governing the use of materials for road construction. A detailed technical characterization of the materials was carried out according to Spanish General Technical Specifications for Road Construction (PG3). The results show that Waelz slag can be adequate for using in granular structural layers, while CDW fits better as granular material in roadbeds. Likewise, fresh MSWI bottom ash can be used as roadbed material as long as it does not contain a high concentration of soluble salts. This paper also discusses the adequacy of using certain traditional test methods for natural soils when characterizing secondary materials for use as aggregates in road construction.     

Seasonal evolution of beach waste and litter during the bathing season on the Catalan coast

Beach waste and litter composition and evolution on popular urban (located in the main nucleus of the municipality) and urbanized (located in residential areas outside the main nucleus) beaches of the Costa Brava (Catalan coast) were assessed during the bathing season. Waste and litter production (amount and composition) were affected by urbanization and varied during the summer. Urban beaches had higher densities of waste deposition and lower percentages of organic, domestic and other miscellaneous waste than urbanized beaches. Litter characteristics were also influenced by type of beach, and varied during the season as a consequence of beach use and cleaning practices, but not environmental factors. Urbanized beaches obtained higher scores for aesthetic quality of sand than urban beaches, and small-sized litter tended to accumulate during the season in the beach of Lloret Centre. The most important problems are management of recyclable materials, litter left by users on the sand, and separation of sand from litter. In addition, current efficiency of mechanical cleaning is low, especially in the withdrawal of cigarette butts. These analyses highlight problems that should be addressed in future management of area beaches.     

Extractability of elements in sugar maple xylem along a gradient of soil acidity

Dendrochemistry has been used for the historical dating of pollution. Its reliability is questionable due primarily to the radial mobility of elements in sapwood. In the present study, the extractability of seven elements was characterized to assess their suitability for the monitoring of environmental conditions. Nine mature sugar maple trees (Acer saccharum Marsh.), a wide-ranging species in eastern North America that has suffered decline in past decades, were sampled in three Quebec watersheds along a soil acidity gradient. Five-year groups of annual tree rings were treated by sequential chemical extractions using extractants of varying strength (deionized H2O, 0.05 M HCl, and concentrated HNO(3)) to selectively solubilize the elements into three fractions (water-soluble, acid-soluble, and residual). Monovalent K; divalent Ba, Ca, Cd, Mg, Mn; and trivalent Al cations were found mostly in the water-soluble, acid-soluble, and residual fractions, respectively. Forms more likely to be mobile within the tree (water-soluble and acid-soluble) do not seem to be suitable for temporal monitoring because of potential lateral redistribution in sapwood rings. However, certain elements (Cd, Mn) were responsive to current soil acidity and could be used in spatial variation monitoring. Extractability of Al varied according to soil acidity; at less acidic sites, up to 90% of Al was contained in the residual form, whereas on very acidic soils, as much as 45% was found in the water-soluble and acid-soluble fractions. Sequential extractions can be useful for determining specific forms of metals as key indicators of soil acidification.     

Effect of mono-ortho and di-ortho substituted polychlorinated biphenyl (PCB) congeners on leopard frog survival and sexual development

We tested the effect of mono-ortho and di-ortho PCB congeners on northern leopard frog (Rana pipiens) hatching success, survival and sexual development. Embryos and tadpoles were exposed to two levels (0.5 and 50 microg/l) of two PCBs. PCBs 101 and 70 were selected because they were present in amphibians collected in the Fox River-Green Bay ecosystem and they have the theoretical structural requirements to be able to bind to the estrogen receptor and mediate estrogenic responses. The exposure of leopard frog embryos and tadpoles to PCB 70 and 101 did not significantly affect hatchability, survival, deformities or growth. There were significant departures from the expected 50:50 sex ratio in tadpoles/froglets exposed to PCB 101 and PCB 70. In all the cases of significant departure, the bias was towards higher number of females. Decrease in the proportion of male gonads and increase in the proportion of intersex gonads were observed with increasing PCB tissue concentrations. The effects of PCB congeners on sexual differentiation occur at concentrations higher than observed in frogs in the Fox River/Green Bay ecosystem.     

Multiscale analysis of heavy metal contents in Spanish agricultural topsoils

This study characterized and mapped the spatial variability patterns of seven topsoil heavy metals (Cr, Ni, Pb, Cu, Zn, Hg and Cd) within the Ebro river basin (9.3 million ha) by Multivariate Factorial Kriging. The variograms and cross-variograms of heavy metal concentrations showed the presence of multiscale variation that was modeled using three variogram models with ranges of 20km (short-range), 100km (medium-range) and 225km (long-range). Our results indicate that the heavy metal concentration is influenced by bedrock composition and dynamics at all the spatial scales, while human activities have a notorious effect only at the short- and medium-range scale of variation. Sources of Cu, Pb and Zn (and secondary Cd) are associated with agricultural practices (at the short-range scale of variation), whereas Hg variation at the short- and medium-range scale of variation is related to atmospheric deposition.     

Mineralization of the biocide chloroxylenol by electrochemical advanced oxidation processes

Electrochemical advanced oxidation processes (EAOPs) are environmentally friendly methods based on the destruction of organic pollutants in wastewaters with in situ electrogenerated hydroxyl radical. This species is formed in anodic oxidation (AO) from water oxidation at the anode and in indirect electro-oxidation methods like electro-Fenton (EF) and photoelectro-Fenton (PEF) also from reaction between catalytic Fe2+ and H2O2 continuously produced at the O2-diffusion cathode. The PEF method involves the irradiation of the treated solution with UVA light to enhance the photolysis of organics including Fe(III) complexes. In this work, the oxidation power of such EAOPs to decontaminate synthetic wastewaters of the biocide chloroxylenol (4-chloro-3,5-dimethylphenol) at pH 3.0 is comparatively examined with an undivided electrolytic cell containing a Pt or boron-doped diamond (BDD) anode and a stainless steel or O2-diffusion cathode. The initial chlorine is released as Cl(-) ion, which remains stable in the medium using Pt or is oxidized to Cl2 on BDD. The biocide solutions can be completely decontaminated using AO with a BDD anode, as well as PEF with a Pt or BDD anode. The PEF procedure with a BDD anode is the most powerful method leading to total mineralization in about 300 min, practically independent of current density. When current density rises, the degradation rate of processes increases, but they become less efficient due to the larger enhancement of waste reactions of oxidants. Chloroxylenol is much more rapidly removed in EF and PEF than in AO. 2,6-dimethylhydroquinone, 2,6-dimethyl-p-benzoquinone and 3,5-dimethyl-2-hydroxy-p-benzoquinone are identified as aromatic by-products, and maleic, malonic, pyruvic, acetic and oxalic acids are found as generated carboxylic acids. A general pathway for chloroxylenol mineralization by all EAOPs including the above by-products is proposed.     

Traffic and catalytic converter - related atmospheric contamination in the metropolitan region of the city of Rio de Janeiro, Brazil

In this work, 24-h PM10 samples were collected in Rio de Janeiro, Brazil, and analysed for trace elements (Cd, Ce, Cu, La, Mo, Ni, Pb, Pd, Rh, Sb and Sn). The sampling was carried out at five locations (Bonsucesso; Centro, downtown city; Copacabana; Nova Igua?u and Sumaré) with different traffic densities and anthropogenic activities. An analytical method based on the EPA method for the determination of trace elements in airborne particulate matter (PM), using ultrasonic-assisted extraction and inductively coupled plasma mass spectrometry (ICP-MS) was applied. Our results suggest that vehicular traffic is the most important source of environmental pollution at the studied sites. The presence of Mo, Pd and Rh in the analysed filters reflects an additional source of pollution caused by the erosion and deterioration of automotive catalytic converters.