Origin,characteristics and morphology of weathering crusts on Istria stone in Venice

To evaluate the effects of the environment on weathering of monuments of Istria stone in Venice, systematic mineralogical, petrographical and elemental analyses of depth profiles were performed on samples of surficial crusts (dendritic black, compact black, grey and white). Decay products of deposition and interactions between gases and stone, including wind blown dust, marine salts, anthropic aerosol, gypsum and nitrates, are incorporated into the mineral matrix down to a depth of 10 mm. In areas sheltered from rain, where black and grey crusts are observed, the high general humidity, carbonaceous particles and deposition of aerosols lead to the development of gypsum and other salts. In compact and grey crusts decay products decrease; in grey crusts carbonaceous particles are reduced, but in compact black crust products of previous treatments are found. In white crusts, formed in areas experiencing effective wash-out, chemical and mechanical attack cause surface recession.     

Classification of dimension stone wastes

Purpose

For countries in which the stone industry is well developed, opposition to quarry and plant waste is gradually increasing. The primary step for waste control and environmental management is to define the problem of concern. In this study, natural building stone wastes were classified for the first time in the literature.

Methods

Following on-site physical observations and research at more than 50 quarries and 20 plants, stone wastes were classified as (1) solid, (2) dust and (3) semi-slurry, slurry and cake.

Conclusions

As a result of this study, the characteristics of wastes, their main environmental threats and the industries in which wastes could be used were defined for each group.     

Application of spectrometric analysis to the identification of pollution sources causing cultural heritage damage

Black crusts are recognized to have been, up to now, one of the major deterioration forms affecting the built heritage in urban areas. Their formation is demonstrated to occur mainly on carbonate building materials, whose interaction with an SO₂-loaded atmosphere leads to the transformation of calcium carbonate (calcite) into calcium sulfate dihydrate (gypsum) which, together with embedded carbonaceous particles, consequently forms the black crusts on the stone surface. An analytical study was carried out on black crust samples collected from limestone monumental buildings and churches belonging to the European built Heritage, i.e., the Corner Palace in Venice (Italy), the Cathedral of St. Rombouts in Mechelen (Belgium), and the Church of St. Eustache in Paris (France). For a complete characterization of the black crusts, an approach integrating different and complementary techniques was used, including laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), Fourier transform infrared spectroscopy, optical and scanning electron microscopy. In particular, the application of LA-ICP-MS permitted to obtain a complete geochemical characterization in terms of trace elements of the black crusts from the inner parts to the external layers contributing to the identification of the major combustion sources responsible for the deterioration over time of the monuments under study. In addition, the obtained results revealed a relation between the height of sampling and the concentration of heavy metals and proved that the crust composition can be a marker to evaluate the variation of the fuels used over time.     

Embryonic sulphated black crusts on carbonate rocks in atmospheric simulation chamber and in the field: role of carbonaceous fly-ash

Experimental conditions characteristic of the urban pollution in many European cities over the last decades were reproduced in a simulation chamber in which samples of limestone were exposed for a period of 12 months, both naked or sprinkled with carbonaceous fly-ash. In agreement with the findings reported in the literature the fly-ash emitted by heavy fuel combustion are highly reactive, undergoing chemical and morphological transformations which give rise to crystals growth, especially gypsum. The development of gypsum crystals was observed overall in close proximity of fly-ash anchoring them to the limestone surface. Samples of the same limestone exposed in the field in a polluted environment for the same period of time led to similar results. The preliminary mechanisms leading to the genesis of sulphated black crusts in polluted environments were thus highlighted. Because of their roughness the embryonic black crusts increase the development of the crust by trapping new particles. This trapping is also facilitated by the wetness of the stone surface leading to the development of hydrated mineral (gypsum) in the water meniscus between fly-ash and stone surface.     

Air pollution records on selenite in the urban environment

Black crusts (BC) on selenite, i.e. gypsum stone used in buildings and monuments in the city of Bologna (northern Italy) have been studied.The crusts have been compared with genetically identical ones encountered on gypsum outcrops in the area surrounding the same city, in a relatively clean rural environment.Because of gypsum's high solubility, also in the past, BC began to form and embed particles of atmospheric aerosol as soon as the stone was used in construction, even though the SO₂ levels in the air were probably much lower than today. Unlike other types of stone (sandstone, limestone, marbles), selenite is currently undergoing a deceleration of dissolution processes, following the acidification of the environment caused by industrialisation. For this reason the BC on selenite are older (up to 580±45 yr), thicker (up to 4 cm) and far more stable than those encountered on other types of building stones used in the same area.The BC are stratified: at the base, in contact with the stone, the crust contains numerous prismatic black particles originating from wood combustion; immediately above the base layer these particles progressively increase; finally, in the outer part of the crust one encounters the characteristic black, spongy spherical fly-ash originating from the combustion of mineral oils.From the chemical point of view, a comparison between urban and rural crusts shows that elements such as C, Si, K, Fe, V, Cr, Ni, Zn, Ga, As and Pb are due to present-day and/or past pollutant sources within the city itself.Moreover, the chemical data from the stratigraphy of the BC show that, while C and K were more abundant in the past than now, elements such as Fe, V, Cr, (Mn, Ni), Cu, (Zn), (Ga), As, Pb characterise recent and current urban atmospheres.     

Microbial regeneration of spent activated carbon dispersed with organic contaminants: mechanism, efficiency, and kinetic models

Background and purpose

Regeneration of spent activated carbon assumes paramount importance in view of its economic reuse during adsorptive removal of organic contaminants. Classical thermal, chemical, or electrochemical regeneration methods are constrained with several limitations. Microbial regeneration of spent activated carbon provides a synergic combination of adsorption and biodegradation.

Methods

Microorganisms regenerate the surface of activated carbon using sorbed organic substrate as a source of food and energy. Aromatic hydrocarbons, particularly phenols, including their chlorinated derivatives and industrial waste water containing synthetic organic compounds and explosives-contaminated ground water are the major removal targets in adsorption?Cbioregeneration process. Popular mechanisms of bioregeneration include exoenzymatic hypothesis and biodegradation following desorption. Efficiency of bioregeneration can be quantified using direct determination of the substrate content on the adsorbent, the indirect measurement of substrate consumption by measuring the carbon dioxide production and the measurement of oxygen uptake. Modeling of bioregeneration involves the kinetics of adsorption/desorption and microbial growth followed by solute degradation. Some modeling aspects based on various simplifying assumptions for mass transport resistance, microbial kinetics and biofilm thickness, are briefly exposed.

Results

Kinetic parameters from various representative bioregeneration models and their solution procedure are briefly summarized. The models would be useful in predicting the mass transfer driving forces, microbial growth, substrate degradation as well as the extent of bioregeneration.

Conclusions

Intraparticle mass transfer resistance, incomplete regeneration, and microbial fouling are some of the problems needed to be addressed adequately. A detailed techno-economic evaluation is also required to assess the commercial aspects of bioregeneration.     

Evaluation of substrate removal kinetics for UASB reactors treating chlorinated ethanes

Purpose

Lack of focus on the treatment of wastewaters bearing potentially hazardous pollutants like 1,1,2 trichloroethane and 1,1,2,2 tetrachloroethane in anaerobic reactors has provided an impetus to undertake this study. The objective of this exercise was to quantify the behavior of upflow anaerobic sludge blanket reactors and predict their performance based on the overall organic substrate removal.

Methods

The reactors (wastewater-bearing TCA (R2), and wastewater-bearing TeCA (R3)) were operated at different hydraulic retention times (HRTs), i.e., 36, 30, 24, 18, and 12?h corresponding to food-to-mass ratios varying in the range of 0.2?C0.7?mg chemical oxygen demand (COD) mg^?1 volatile suspended solids day^?1. The process kinetics of substrate utilization was evaluated on the basis of experimental results, by applying three mathematical models namely first order, Grau second order, and Michaelis-Menten type kinetics.

Results

The results showed that the lowering of HRT below 24?h resulted in reduced COD removal efficiencies and higher effluent pollutant concentrations in the reactors. The Grau second-order model was successfully applied to obtain the substrate utilization kinetics with high value of R ² (>0.95). The Grau second-order substrate removal constant (K ₂) was calculated as 1.12 and 7.53?day^?1 for reactors R2 and R3, respectively.

Conclusion

This study demonstrated the suitability of Grau second-order kinetic model over other models, for predicting the performance of reactors R2 and R3, in treating wastewaters containing chlorinated ethanes under different organic and hydraulic loading conditions.     

Characteristics of an aerobic denitrifier that utilizes ammonium and nitrate simultaneously under the oligotrophic niche

Introduction

An aerobic denitrifier was isolated from the Hua-Jia-Chi pond in China and identified as Pseudomonas mendocina 3-7 (Genbank No. HQ285879). This isolated strain could express periplasmic nitrate reductase which is essential for aerobic denitrification occurred when the dissolved oxygen (DO) level maintains at 3?C10?mg?L^?1.

Methods

To determine whether the ability of isolated strain is exhibited in the bioremediation of polluted drinking source water, the heterotrophic nitrification and aerobic denitrification characteristics of P. mendocina 3-7 under different cultural conditions such as oxygen level, nitrate and organic concentrations were studied from the nitrogenous balance in the paper.

Results and conclusions

By measuring the nitrogen balance in all experiments under different culture conditions, the removal of total organic carbon and ammonium was positively correlated with total nitrogen removal, especially under high substrate level. With substrate concentration decreasing, ammonium and nitrate removal occurred separately, and ammonium was completely utilized first under low substrate concentration. Compared to that under high substrate level, the specific growth rate of P. mendocina 3-7 was not low under the low substrate level and the pollutant removal efficiencies remained high, which implies the stronger nitrogen removal and acclimatization capacities of the strain in oligotrophic niches.     

Acute effect of benzo[a]anthracene on the biodegradation of peptone under aerobic conditions

Background

This study investigated the acute effect of benzo[a]anthracene, a significant compound among polycyclic aromatic hydrocarbons, on the biodegradation of a synthetic organic substrate??a peptone/meat extract mixture??under aerobic conditions.

Methods

A laboratory-scale sequencing batch reactor was sustained at steady state at a sludge age of 10?days with substrate feeding. Inhibition tests involved running a series of batch reactors initially seeded with the biomass obtained from the parent reactor. After the biomass seeding, the reactors were started with the peptone mixture and a range of initial benzo[a]anthracene concentrations between 0.5 and 88?mg/L. Experimental profiles of oxygen uptake rates and polyhydroxyalkanoates were evaluated by calibration of a selected model.

Results

Lower doses of benzo[a]anthracene had no effect on process kinetics. The noticeable acute impact was only observed with the addition of 88?mg/L of benzo[a]anthracene, but it was limited with the storage mechanism: the amount of organic substrate diverted to polyhydroxyalkanoates was significantly reduced with a corresponding decrease in the maximum storage rate, k _STO, from 2.7 down to 0.6?day^?1. Similarly, the maximum growth rate from internally stored polyhydroxyalkanoates was lowered from 2.3 to 1.0?day^?1.

Conclusion

Among the mechanisms for direct substrate utilization, only the hydrolysis rate was slightly reduced, but otherwise, the overall COD removal efficiency was not affected.     

Effect of particle size of titanium dioxide nanoparticle aggregates on the degradation of one azo dye

Introduction

Titanium dioxide (TiO₂) nanoparticle powders have been extensively studied to quickly photodegrade some organic pollutants; however, the effect of the particle size of TiO₂ nanoparticle aggregates on degradation remains unclear because microscale aggregates form once the nanoparticle powders enter into water.

Methods

The degradation of azo dye by different particle sizes of TiO₂ nanoparticle aggregates controlled by NaCl concentrations was investigated to evaluate the particle size effect. Removal reactions of reactive black 5 (RB5) with TiO₂ nanoparticles followed pseudo-first-order kinetics.

Results

The increase of TiO₂ dosage from 40 to 70?mg/L enhanced the degradation. At doses around 100?mg/L TiO₂, degradation rates decreased which could be the result of poor UV light transmittance at high-particle concentrations. At average particle sizes of TiO₂ nanopowders less than around 500?nm, the degradation rates increased with decreasing particle size. As the average particle size exceeded 500?nm, the degradation rates were not significantly changed.

Conclusions

For the complete degradation experiments, the mineralization rates of total organic carbon disappearance are generally following the RB5 decolorization kinetic trend. These findings can facilitate the application of TiO₂ nanoparticles to the design of photodegradation treatments for wastewater.     

Application of laser ablation ICP-MS and traditional techniques to the study of black crusts on building stones: a new methodological approach

Introduction  

In this work, we propose an innovative application of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) as a methodological approach for the chemical characterisation of black crusts on stone monuments, associated with traditional micro-morphological (optical and scanning electron microscopy) and infrared spectroscopic techniques (FTIR).     

Photocatalytic degradation of methyl orange by a multi-layer rotating disk reactor

Introduction

Solar wastewater treatment based on photocatalytic reactions is a green process that utilizes renewable energy resources and minimizes secondary pollution. Reactor design plays an important role in promoting treatment efficiency and throughput density (based on unit volume of the reactor).

Experimental

A rotating disk reactor that significantly increases the process efficiency has been designed and evaluated for application to photocatalytic decomposition of dye pollutants in aqueous solutions. In this process, a novel multi-layer rotating disk reactor (MLRDR) was presented. Photocatalyst (TiO₂) particles are immobilized on the surfaces of disks. Within each layer of the reactor, methyl orange aqueous solution is allowed to flow from the center of the disk in a radial direction along the surface of the disk, which is rotating at high speed and is irradiated with UV lamps. The effluent is then directed to the center of another layer that lies underneath. Up to four stacked layers have been tested in this study, and the effects due to the number of the layers and volumetric flow rate on reaction conversion are investigated.

Results and discussion

The efficiency of this photocatalytic reactor exhibits complex dependence on these parameters. With selected operating conditions, conversions greater than 95% can be achieved within seconds of residence time. Design equations of the reactor have been derived based on fluid dynamics and kinetic models, and the simulation results show promising scale-up potential of the reactor.     

Evolutions of microbial degradation pathways for parent xenobiotic and for its metabolites follow different schemes

Background and purposes

The pathways used by microorganisms for the metabolism of every xenobiotic substrate are specific. The catabolism of a xenobiotic goes through a series of intermediate steps and lower intermediates (metabolites) appear in sequence. The structure of the metabolites can be similar to the parents due to kinship. The purposes of this study were to examine if the degradation pathways that were developed for a parent xenobiotic are effective to degrade the parent??s lower metabolites, and if the reverse is true.

Materials and methods

The xenobiotic substrates, 2,4-dichlorophenoxyacetic acid (2,4-D, the parent xenobiotic) and its metabolite 2,4-dichlorophenol (2,4-DCP), were independently subjected to acclimation and degradation tests by the biomasses of mixed-culture activated sludge and a pure culture of Arthrobacter sp.

Results

Activated sludge and Arthrobacter sp. that were acclimated to 2,4-D effectively degraded 2,4-D and the lower metabolites of 2,4-D, typically 2,4-DCP. During the degradation of 2,4-D, accumulations of the lower metabolites of 2,4-D were not found. The degradation pathways acquired from acclimation to 2,4-D are effective for all the metabolites of 2,4-D. However, pathways acquired from acclimation to 2,4-DCP are not effective in the degradation of the parent 2,4-D.

Conclusions

Microorganisms acclimated to 2,4-D evolve their degradation pathways by a scheme that is different from the scheme the microorganisms employ when they are acclimated to the metabolites of 2,4-D.     

Photocatalytic degradation of gaseous toluene by using immobilized titania/silica on aluminum sheets

Purpose

The aim of this study was to prepare a highly active immobilized titania/silica photocatalyst and to test its performance in situ toward degradation of toluene as one of the major toxic indoor contaminants.

Methods

In this work, two different titania layers immobilized on Al sheets were synthesized via low temperature sol?Cgel method employing presynthesized highly active titania powders (Degussa P25 and Millennium PC500, mass ratio 1:1): (a) with a silica/titania binder and a protective layer and (b) without the binder. The photocatalysts were characterized by X-ray diffraction, nitrogen sorption measurements, scanning electron microscopy (SEM), infrared spectroscopy, and UV?Cvis diffuse reflectance spectroscopy (DRS). The in situ photocatalytic degradation of gaseous toluene was selected as a probe reaction to test photocatalytic activity and to verify the potential application of these materials for air remediation.

Results

Results show that nontransparent highly photocatalytically active coatings based on the silica/titania binder and homogeneously dispersed TiO₂ powders were obtained on the Al sheets. The crystalline structure of titania was not altered upon addition of the binder, which also prevented inhomogeneous agglomeration of particles on the photocatalyst surface. The photoactivity results indicate that the adsorption properties and photocatalytic activity of immobilized photocatalysts with the silica/titania binder and an underlying protective layer were very effective and additionally, they exhibited considerably improved adhesion and uniformity.

Conclusion

We present a new highly photocatalytically active immobilized catalyst on a convenient metallic support, which has a potential application in an air cleaning device.     

Composition of weathering crusts on sandstones from natural outcrops and architectonic elements in an urban environment

This work presents mineralogical and chemical characteristics of weathering crusts developed on sandstones exposed to various air pollution conditions. The samples have been collected from sandstone tors in the Carpathian Foothill and from buildings in Kraków. It has been stated that these crusts differ in both fabric and composition. The sandstone black crust from tors is rich in organic matter and composed of amorphous silica. Sulphate incrustations accompanied by dust particles have been only sometimes observed. Beneath the black crust, a zone coloured by iron (oxyhydr)oxides occurs. The enrichment of the surface crust in silica and iron compounds protects the rock interior from atmospheric impact. The sandstones from architectonic details are also covered by a thin carbon-rich black crust, but they are visibly loosened. Numerous salts, mainly gypsum and halite, crystallise here, thus enhancing deterioration of the rock. Moreover, spherical particles originated from industrial emissions are much more common. Gypsum in natural outcrops, forms isolated and well-developed crystals, whilst these found on the architectonic details are finer and densely cover the surface. Such diversity reflects various concentrations of acid air pollutants in solutions.     

Identification of volatiles from Pinus silvestris attractive for Monochamus galloprovincialis using a SPME-GC/MS platform

Introduction

A myriad of volatile organic compounds (VOCs) released by terrestrial vegetation plays an important role in environmental sciences. A thorough chemical identification of these species at the molecular level is essential in various fields, ranging from atmospheric chemistry to ecology of forest ecosystems. In particular, the recognition of VOCs profiles in a context of plant?Cinsect communication is a key issue for the development of forest protection tools.

Purpose

This work was aimed at the development of a simple, robust and reliable method for the identification of volatiles emitted from plant materials, which can attract or deter pest insects. Specifically, volatiles emitted from the bark of Pinus sylvestris were studied, which might attract the black pine sawyer beetle Monochamus galloprovincialis??a serious pest of the tree and a vector of a parasitic nematode Bursaphelenchus xylophius.

Method

The volatiles from bark samples were collected using a solid-phase micro-extraction technique, and subsequently analysed by gas-chromatography/mass-spectrometry (GC/MS). The characterisation of the volatile fraction was based on the comparison with data in mass spectral libraries, and in most cases, with the available authentic standards. The identified compounds were screened against the available entomological data to select insect attractors.

Results

The identified components included terpenes (??-pinene, ?-3-carene, and para-cymenene), oxygenated terpenes (??-terpineol and verbenone), sesquiterpenes (??-longipinene, longifolene, E-??-farnesene, ??-cadinene and pentadecane), and diterpenes (manoyl oxide and (+)-pimaral). Of these, longifolene and (+)-pimaral are of particular interest as plausible attractors for the M. galloprovincialis beetle that might find application in the construction of insect bait traps.     

Aquatic photochemistry of paracetamol in the presence of dissolved organic chromophoric material and nitrate

Purpose

This study contains some new findings connected to the photolysis of the drug paracetamol (hereinafter APAP) especially in light of estimating natural conditions, and it will offer information to better evaluate environmental problems connected with this widely used analgesic agent. Only a few studies, so far, have focussed on the photodegradation process of APAP in the natural environment, and the question about the role of the colored/chromophoric dissolved organic matter (CDOM) and nitrate (NO ₃ ^? ) as photoinductors is almost open.

Methods

APAP dissolved in freshwater and pure laboratory water in the presence and absence of CDOM and NO ₃ ^? ions was irradiated using weak-energy photon energies simulating natural conditions.

Results

CDOM and NO ₃ ^? as photoinductors produced only the slow phototransformation of APAP under weak energy radiation, and APAP seemed to be practically resistant to direct photolysis under weak radiant energies available in natural conditions. The estimated reaction efficiencies, in addition to half-lives, speak for that NO ₃ ^? and CDOM do not act as quite independent photoinductors but their effect in conjunction (CDOM?CNO ₃ ^? ?Cwater) is stronger than the separate ones. The principal phototransformation intermediates of APAP were mono-hydroxy derivatives, depending on available photon energies formed via ortho- or meta-hydroxylation, possessing substantial power of resistance to further specific transformation reactions.

Conclusions

The estimated half-life of the phototransformation of APAP in the natural aqueous environment and in the presence of suitable photoinductors will be about 30?days or more.     

Seed bank persistence of genetically modified canola in California

Introduction

Canola, which is genetically modified (GM) for tolerance to glyphosate, has the potential to become established as a new glyphosate resistant weed, thus reducing the effectiveness of glyphosate.

Methods

Volunteer from dormant canola seeds produced thousands of plants per hectare in the fourth year (2011) following a 2007 crop harvest. This occurred with no additional canola seed production since the 2007 harvest.

Results

Volunteer plants following harvests of annual crops are typically only a problem for the first year after harvest. In California, glyphosate is the core herbicide on over a million hectares of high value row, tree, and vine crops and new glyphosate resistant weeds reduce the effectiveness of glyphosate.

Conclusions

The combination of dormant seed and herbicide resistance makes GM glyphosate-resistant canola a new and difficult California weed which was first observed in the winter of 2009.     

Source apportionment of ultrafine and fine particle concentrations in Brisbane, Australia

Purpose

To investigate the significance of sources around measurement sites, assist the development of control strategies for the important sources and mitigate the adverse effects of air pollution due to particle size.

Methods

In this study, sampling was conducted at two sites located in urban/industrial and residential areas situated at roadsides along the Brisbane Urban Corridor. Ultrafine and fine particle measurements obtained at the two sites in June?CJuly 2002 were analysed by positive matrix factorization.

Results

Six sources were present, including local traffic, two traffic sources, biomass burning and two currently unidentified sources. Secondary particles had a significant impact at site 1, while nitrates, peak traffic hours and main roads located close to the source also affected the results for both sites.

Conclusions

This significant traffic corridor exemplifies the type of sources present in heavily trafficked locations and future attempts to control pollution in this type of environment could focus on the sources that were identified.     

Improvement of biodegradability of PVA-containing wastewater by ionizing radiation pretreatment

Background

Polyvinyl alcohol (PVA) has been widely used as sizing agents in textile and manufacturing industry, and it is a refractory compound with low biodegradability.

Objective

The objective of this paper was to treat the PVA-containing wastewater using gamma irradiation as a pretreatment strategy to improve its biodegradability and to determine the roles of different kinds of radical species played during pretreatment.

Methods

Gamma radiation was carried out in a ⁶⁰Cobalt source station, PVA concentration was analyzed by using a visible spectrophotometer and specific oxygen uptake rate (SOUR, milligram of O₂ per gram of mixed liquor volatile suspended solids (MLVSS) per hour) was measured by a microrespirometer.

Results

The results showed that the biodegradability of PVA-containing wastewater with low initial concentration (e.g., 327.8?mg/l) could be improved greatly with increasing irradiation dose. However, PVA gel formation was observed at higher initial PVA concentration (e.g., 3,341.6?mg/l) and higher irradiation dose, which inhibited PVA degradation by aerobic microorganisms. However, the formed gel could be separated by microfiltration, which led to more than 90% total organic carbon (TOC) removal.

Conclusion

Ionizing radiation could be used as a pretreatment technology for PVA-containing wastewater, and its combination with biological process is feasible.