Upgrading Pyrolytic Oil via Catalytic Co-Pyrolysis of Beechwood and Polystyrene.

This study aims to investigate the catalytic co-pyrolysis of beech wood with polystyrene as a synergic and catalytic effect on liquid oil production. For this purpose, a tubular semi-continuous reactor under an inert nitrogen atmosphere was used. Several zeolite catalysts were modified via incipient wetness impregnation using iron and/or nickel. The liquid oil recovered was analyzed using GC-MS for the identification of the liquid products, and GC-FID was used for their quantification. The effects of catalyst type, beechwood-to-polystyrene ratio, and operating temperature were investigated. The results showed that the Fe/Ni-ZSM-5 catalyst had the best deoxygenation capability. The derived oil was mainly constituted of aromatics of about 92 wt.% for the 1:1 mixture of beechwood and polystyrene, with a remarkably high heating value of around 39 MJ/kg compared to 18 MJ/kg for beechwood-based bio-oil. The liquid oil experienced a great reduction in oxygen content of about 92% for the polystyrene-beechwood 50-50 mixture in comparison to beechwood alone. The catalytic and synergetic effects were more realized for high beechwood percentages as a 75-25 beechwood-polystyrene mix. Regarding the temperature variation between 450 and 600 °C, the catalyst seemed to deactivate faster at higher temperatures, thus constituting a quality reduction in the pyrolytic oil in high-temperature ranges.

Phytochemical and pharmacological properties of essential oils from Cedrus species.

Natural products frequently exert pharmacological activities. The present review gives an overview of the ethnobotany, phytochemistry and pharmacology of the Cedrus genus, e.g. cytotoxic, spasmolytic immunomodulatory, antiallergic, anti-inflammatory and analgesic activities. Cancer patients frequently seek remedies from traditional medicinal plants that are believed to exert less side effects than conventional therapy with synthetic drugs. A long-lasting goal of anti-cancer and anti-microbial therapy research is to find compounds with reduced side effects compared to currently approved drugs. In this respect, Cedrus species might be of interest. The essential oil isolated from Cedrus libani leaves may bear potential for drug development due to its high concentrations of germacrene D and ß-caryophyllene. The essential oils from Cedrus species also show bioactivity against bacteria and viruses. More preclinical analyses (e.g. in vivo experiments) as well as clinical trials are required to evaluate the potential of essential oils from Cedrus species for drug development.

Iron mineralogy as a fingerprint of former steelmaking activities in river sediments.

Submerged sediment cores were collected upstream of a dam in the Orne River, northeastern France. This dam was built in the context of steelmaking to constitute a water reservoir for blast furnace cooling and wet cleaning of furnace smokes. The dam also enhanced sediment deposition in the upstream zone. This study was performed to unravel the contamination status of sediments and to evidence possible contribution sources. The sediment layers were analyzed for water content, grain size, chemical composition, crystalline phases at a bulk scale and poorly crystalline and amorphous phases at a sub-micrometer scale. Visual aspect, texture, color, and chemical and mineralogical analyses showed that the settled sediments were mainly composed of fine black matter, certainly comprising steelmaking by-products. Those materials were highly enriched with Fe, Zn, Pb and other trace metals, except for a relatively thin layer of surficial sediments that had settled more recently. Bulk mineralogy revealed crystalline iron minerals, such as magnetite, goethite, wuestite and pyrite, in the deep layers of the sediment cores. Furthermore, microscopic investigations evidenced the presence of ferrospheres, goethite nanoparticles and newly formed Fe-aluminosilicates; all originating from the former steelmaking facilities. The variation of iron mineralogy, combined with specific chemical profiles and other sediment features, demonstrate the different contributions that constitute the sediment deposit. Furthermore, chemical and mineralogical features of goethite and Fe-aluminosilicates could be used as a fingerprint for such contaminated sediments.

Hydrodynamic influence on reservoir sustainability in semi-arid climate: A physicochemical and environmental isotopic study.

Water scarcity and increasing water demand require the development of water management plans such as establishing artificial lakes and dams. Plans to meet water needs are faced by uprising challenges to improve water quality and to ensure the sustainability of hydro-projects. Environmental isotopes coupled to water physicochemical characteristics were investigated over a biennial cycle to assess both geomorphological and environmental impacts on the water quality of a reservoir situated in an intensively used agricultural watershed under a Mediterranean semi-arid climate. The particularity of the semi-arid climate and the diverse topography generate a continental and orographic rain effect on the isotopic composition of precipitation and the water recharged sources. The studied reservoir responds quickly to land-use activities and climatic changes as reflected by temporal and spatial variations of water chemistry and isotopic composition. Increasing changes in precipitation rate and dry periods significantly modified the water isotopic composition in the reservoir. During the first year, hydrogen (δD) and oxygen (δ18O) isotopes are depleted by 6 and 2‰ between dry and wet season, respectively. While a shift of -2‰ for δD and -1‰ for δ18O was detected during the second annual cycle. Environmental isotopic compositions demonstrate for the first time the occurrence of groundwater inflow to the central (Cz) and dam (Dz) zones of the Qaraaoun reservoir. The Cz and Dz can be considered as open water bodies subjected to dilution by groundwater inflow, which induces vertical mixing and reverse isotopic stratification of the water column. In the contrary, the river mouth zone acts as a closed system without groundwater intrusion, where heavy water accumulates and may act as a sink for contaminants during dry season. Groundwater influx acts as a dilution factor that renews the hypolimnion, and minimizes the perturbations induced by both internal biogeochemical reactions and external hydrological variations. Attention should be devoted to the hydrogeological location of planned reservoirs, which should take into account the vicinity of shallow water table to insure good water quality and water sustainability.

Lead bioaccumulation in Opuntia ficus-indica following foliar or root exposure to lead-bearing apatite.

The contamination of edible leafy vegetables by atmospheric heavy metal-bearing particles is a major issue in environmental toxicology. In this study, the uptake of lead by cladodes of Opuntia ficus-indica (Ofi), traditionally used in Mexican cuisine and in livestock fodder, is investigated after a 4-months exposure of either cladodes or roots to synthetic Pb-fluorapatite particles. Atomic Absorption Spectroscopy (AAS) for the quantitative analysis of Pb levels, Scanning Electron Microscopy coupled with Energy Dispersive X-Ray Spectroscopy (SEM-EDX) for the examination of the cladode surface and fate of particles, and Micro-X-ray fluorescence (µXRF) measurements for elemental mapping of Pb in cladodes, were used. The results evidence that foliar contamination may be a major pathway for the transfer of Pb within Ofi cladodes. The stomata, areoles, and cuticle of cladode surface, play an obvious role in the retention and the incorporation of lead-bearing apatite, thus revealing the hazard of eating contaminated cladodes. The possibility of using series of successive cladodes for biomonitoring the atmospheric pollution in arid and semi-arid regions is also rapidly discussed.

Role of phosphogypsum and NPK amendments on the retention or leaching of metals in different soils.

Column leaching tests were conducted to investigate the effects of soil physicochemical characteristics on metal mobility in the subsurface. The metals investigated originated from disposed industrial waste byproducts and from agrochemicals spread over the farmlands. Soil column tests can provide insights into leaching of metals to underlying water compartments. The findings of this study can be used for prevention strategies and for setting risk assessment approaches to land-use and management, and soil and water quality and sustainability. Soils collected from an industrial (IS) watershed and an agricultural (AQ) hydrographic basin were used in soil column leaching experiments. The soil samples were characterized for mineralogy, functional groups, grain size, surface charge, soil type, porosity, and cation exchange capacity (CEC) along with elemental composition. Varying concentrations of phosphogypsum industrial waste or agrochemical (NPK fertilizer) was then added to the surface of the packed columns (n = 28). The columns were subjected to artificial rain over a period of 65 days. Leachates were collected and analyzed for dissolved Na(+), K(+), and Cd(2+) throughout the experimental period, whereas residual Cd content in the subsurface soil was measured at the end of the experiment. Physicochemical characterization indicated that the AQ soil has a higher potential for metal retention due to its fine clay texture, calcareous pH, high organic matter content and CEC. Metal release was more prominent in the IS soil indicating potential contamination of the surrounding soil and water compartments. The higher metal release is attributed to soil physicochemical characteristics. High calcium concentrations of phosphogypsum origin is expected to compete for adsorbed bivalent elements, such as Cd, resulting in their release. The physicochemical characteristics of the receiving media should be taken into consideration when planning land-use in order to achieve sustainable development. Soil physiochemical characteristics play a key role in determining the behavior and fate of elements upon application of amendments. Sandy soils should not be assigned to industrial zones or landfills due to their high permeability, unlike fine clay soils. Furthermore, application of fertilizers on sandy soils can threaten groundwater quality, whereas their extensive use on clayey soil can cause soil salinisation.

Reservoir sediments: a sink or source of chemicals at the surface water-groundwater interface.

This study delineates the physical, chemical, and biological effects resulting from anthropogenic and endogenic activities in a sensitive dammed reservoir situated in a semi-arid region. The reservoir is characterized by two major flow regimes: a wet fill hydrologic regime and a dry spill one. A seasonal sampling campaign was carried out over a period of 2 years (2011-2013) where water samples were collected across the water column and from piezometers just outside the perimeter of the reservoir. Similarly, sediments were collected from the corresponding areas beneath the water column. The water samples were analyzed for environmental isotopic ratios, elemental composition, and physical, biological and chemical parameters, whereas the sediment and algal samples were subjected to physical, mineralogical, spectroscopic, and microscopic analyses. This investigation indicated that the dam had resulted in the alteration of the biogeochemical cycle of nutrients as well as the degradation of the sediment and water quality. The hydrological and biogeochemical processes were found to induce vertical downward transport of chemicals towards the fine grained calcareous sediments during the fill mode, whereas the sediments acted as a source of a chemical flux upward through the water column and downward towards the groundwater during the spill mode. The geomorphological characteristics of the reservoir enhanced the strong hydrological connectivity between the surface water and the groundwater where the reservoir responded quickly to natural and anthropogenic changes in the upper watershed. The water and sediments in the sensitive spill mode were of poor quality and should receive more attention due to the potential hazard for the associated hydro-project and the sustainability of the agricultural soil in the long term. Thus, a safe water and sediment management plan should be implemented in order to improve the dam functionality and to safeguard the precious water resources.

Potential of Opuntia ficus-indica for air pollution biomonitoring: a lead isotopic study.

Opuntia ficus-indica (Ofi) is a long-domesticated cactus that is widespread throughout arid and semiarid regions. Ofi is grown for both its fruits and edible cladodes, which are flattened photosynthetic stems. Young cladodes develop from mother cladodes, thus forming series of cladodes of different ages. Therefore, successive cladodes may hold some potential for biomonitoring over several years the local atmospheric pollution. In this study, cladodes, roots, dust deposited onto the cladodes, and soil samples were collected in the vicinity of three heavily polluted sites, i.e., a fertilizer industry, the road side of a highway, and mine tailings. The lead content was analyzed using atomic absorption spectroscopy (AAS) and inductively coupled plasma-mass spectrometry (ICP-MS). Scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDX) was used to characterize the cladode surfaces and the nature of dust deposit, and the lead isotopes were analyzed to identify the origin of Pb. The results show that (i) Ofi readily bioaccumulates Pb, (ii) the lead isotopic composition of cladodes evidences a foliar pathway of lead into Ofi and identifies the relative contributions of local Pb sources, and (iii) an evolution of air quality is recorded with successive cladodes, which makes Ofi a potential biomonitor to be used in environmental and health studies.

Metal binding in soil cores and sediments in the vicinity of a dammed agricultural and industrial watershed.

The environment is witnessing a downgrade caused by the amelioration of the industrial and agricultural sectors, namely, soil and sediment compartments. For those reasons, a comparative study was done between soil cores and sediments taken from two locations in the Qaraaoun reservoir, Lebanon. The soil cores were partitioned into several layers. Each layer was analyzed for several physicochemical parameters, such as functional groups, particle size distribution, ζ-potential, texture, pH, electric conductivity, total dissolved solids, organic matter, cation exchange capacity, active and total calcareous, available sodium and potassium, and metal content (cadmium, copper, and lead). The metal content of each site was linked to soil composition and characteristics. The two sites showed distinguishable characteristics for features such as organic matter, pH, mineral fraction, calcareous, and metal content. The samples taken toward the south site (Q1), though contain lower organic matter than the other but are more calcareous, showed higher metal content in comparison to the other site (Q2) (average metal content of Q1 > Q2; for Cd 3.8 > 1.8 mg/kg, Cu 28.6 > 21.9 mg/kg, Pb 26.7 > 19 mg/kg). However, the metal content in this study did not correlate as much to the organic matter; rather, it was influenced by the location of the samples with respect to the dam, the reservoir's hydrodynamics, the calcareous nature of the soil, and the variation of the industrial and agricultural influence on each site.

First assessment of triclosan, triclocarban and paraben mass loads at a very large regional scale: case of Paris conurbation (France).

The objective of this study was to examine the occurrence of parabens (5 congeners), triclosan (TCS) and triclocarban (TCC) at the scale of the Parisian sewer network and to provide representative knowledge on these compounds in France for a large area. For this purpose and in collaboration with the Parisian public sanitation service (SIAAP) in charge of the collect and treatment of the Parisian wastewater, this study focused on seven main sewer trunks of the Paris conurbation, accounting for 1900,000 m(3) d(-1), i.e., about 8 million inhabitants. Concentrations lying in the 2000-20000 ng l(-1) ranges were found in wastewater, confirming the ubiquity of parabens, TCS and TCC in our environment and household products. Parabens (>97%) and to a lesser extent TCS (68% in median) were mainly associated to the dissolved fraction, as demonstrated by low KD and KOC values. For the first time, this study also evaluated the pollutant mass loads per population equivalent (PE) of parabens, TCS and TCC at the large and representative scale of the Parisian conurbation. Hence, the median mass loads varied from 176 to 3040 µg PE(-1) d(-1) for parabens and from 26 to 762 µg PE(-1) d(-1) for TCS and TCC. Based on these results and according to the assumptions done, the extrapolation of the mass loads at the national scale pointed out an annual mass loads between 51.8 and 100.7 ty(-1) for methyl paraben (MeP) and between 11.2 and 23.5 ty(-1) for TCS. Mass loads per equivalent habitant and national mass loads are both extremely relevant and innovative data. Contrary to other countries, such data are nowadays rather difficult to gain in France and neither enquiry nor database provides access to information on the use and production of these chemicals. Since cosmetic industries are voluntarily and fully engaged in the substitution of parabens, triclosan and triclocarban in personal care product, this study could constitute a "time reference status" which could be used as a basis for future monitoring.

Applying physicochemical approaches to control phosphogypsum heavy metal releases in aquatic environment.

One of the most important sources of solid waste in the Mediterranean Basin ecosystem originated from the phosphate fertilizer industries, which discharge phosphogypsum (PG) directly into aquatic environments or are stacked on stockpiles. The present study investigates metal release from PG under the influence of variable pH, increasing PG mass content, and complexing organic matter ligands. Major ions from PG leachates, grain size and charge, main functional groups along with metal leachability (Pb, Cd, Cr, Cu, and Zn) were determined using ion chromatography, laser diffraction, zetameter, Fourier transform infrared spectroscopy, and atomic absorption spectroscopy, respectively. The complete dissolution of PG recorded is at 2 g/L. Saturation and supersaturation with respect to PG may occur at concentrations of 3 and 4 g/L, respectively, revealing a clustering phenomenon leading to heavy metal encapsulation within the aggregates. Organic ligands such as citrate may trigger the cationic exchange within the PG suspension leading to ion release. As these factors are considered as specific process involving the release of contaminants from PG during storage under natural conditions, this study could set the foundations for PG remediation in aquatic environment. Organic ligands under controlled pH conditions could be utilized in treating fertilizer industrial wastes by taking into consideration the particularity of the receiving area, thus decreasing metal hazardous impact on natural media.

Disruption of biofilms from sewage pipes under physical and chemical conditioning.

Biofilms grown inside two sewage collecting pipes located in industrial and residential areas are studied. Bacterial biomass inside three layers of biofilms was evaluated. Biofilm cohesion under different mixing rate and ionic strength was also investigated. Effects of physical and chemical parameters in the biofilms were evaluated by monitoring turbidity, chemical and biochemical oxygen demands. Extracted organic matter from biofilms was partitioned to polar, aromatic and saturated fractions using activated silica column chromatography. Results revealed that bacterial biomass growth depending on biofilm thickness and stratification. The most loaded stratum in bacterial biomass was the sewage-biofilm interface stratum that represented 51% of the total bacterial biomass. Stirring rate and ionic strength of mono- and bivalent salts showed a major influence in biofilm disruption. The stirring time enhanced the exchange dynamic and matter capture between biofilm fragments at the critical stirring rate 90 r/min. Sodium chloride showed the dispersing effect on biofilms in suspension, and decreased the BOD5 (biochemical oxygen demand) beyond the physiological salt concentration.