Biospheric influence on carbon dioxide measurements in Italy

The study concerning carbon dioxide measurements taken during the 1997, 1998 and 1999 summer campaigns at two different altitude stations and biospheric conditions are presented. The higher station (Mt. Cimone, 2165 m a.s.l.) is characterised by 360° free horizon and is located on a rocky mountain while the lower (Ninfa lake, 1550 m a.s.l.) is located inside the red spruce and beech forest. The different behaviour of CO₂ at the two mountain stations has been registered. It shows the strong effect of nighttime soil emission and vegetation respiration on CO₂ mixing ratio increases and of diurnal vegetative activity on CO₂ concentration decreases at the lower measurement site. The baseline character of the higher measurement site has been confirmed by comparison of CO₂ diurnal amplitudes recorded at the two stations.     

Comparison of the degradation of p-hydroxybenzoic acid in aqueous solution by several oxidation processes

A comparative study is made of 12 methods of chemical oxidation applied to degrading p-hydroxybenzoic acid in aqueous solution. The oxidation processes tested were: UV, O3, UV/TiO2, O3/Fe2+, O3/H2O2, O3/UV, UV/H2O2, H2O2/Fe2+, H2O2/Fe2+/O3, UV/H2O2/O3, H2O2/Fe2+/UV and O3/UV/H2O2/Fe2+. The 12 processes were ranked by reactivity. In a kinetic study, the overall kinetic rate constant was split up into three components: direct oxidation by UV irradiation (photolysis), direct oxidation by ozone (ozonation), and oxidation by free radicals (mainly OH*).     

Nutrient losses by surface run-off following the application of organic manures to arable land. 2. Phosphorus

Phosphorus (P) surface run-off losses were studied following organic manure applications to land, utilising a purpose-built facility on a sloping site in Herefordshire under arable tillage. Different rates and timing of cattle slurry, farm yard manure (FYM) and inorganic nitrogen (N) and P fertiliser were compared, over a 4-year period (1993-97). N losses from the same studies are reported in a separate paper. The application of cattle FYM and, especially slurry, to the silty clay loam soil increased both particulate and soluble P loss in surface water flow. Losses via subsurface flow (30 cm interflow) were consistently much lower than via surface water movement and were generally unaffected by treatment. Increased application of slurry solids increased all forms of P loss via surface run-off; the results suggested that a threshold for greatly increased risk of P losses via this route, as for N, occurred at ca. 2.5-3.0 t/ha solids loading. This approximates to the 50 m3/ha application rate limit suggested for slurry within UK 'good agricultural practice'. The studies also provided circumstantial evidence of the sealing of the soil surface by slurry solids as the major mechanism by which polluting surface run-off may occur following slurry application on susceptible soils. Losses of total and soluble P, recorded for each of the 4 years of experiments, reached a maximum of only up to 2 kg/ha total P (TP), even after slurry applications initiating run-off. Whilst these losses are insignificant in agronomic terms, peak concentrations of P (up to 30,000 micrograms/l TP) in surface water during a run-off event, could be of considerable concern in sensitive catchments. Losses of slurry P via surface run-off could make a significant contribution to accelerated eutrophication on entry to enclosed waters, particularly when combined with high concentrations of NO3(-)-N. Restricting slurry application rates to those consistent with good agronomic practice, and within the limits specified in existing guidelines on good agricultural practice, offers the simplest and most effective control measure against this potentially important source of diffuse pollution.     

Immunotoxicity risks associated with land-treatment of petrochemical wastes revealed using an in situ rodent model

Land-treatment of petrochemical wastes is a widely used method to dispose of hazardous and non-hazardous waste by biodegradation. However, no comprehensive assessment of the impact of such disposal techniques on terrestrial ecosystems has been conducted. Despite the presence of suspected immunotoxicants in the soil, wild rodents frequently reside on these waste sites after closure or abandonment. We explored the seasonal sensitivity of the immune system of the hispid cotton rat (Sigmodon hispidus) to in situ exposures on sites land-treated with petrochemical wastes. Animals were monitored on five contaminated land-treatment sites and five ecologically matched-reference sites in Oklahoma, USA, over two seasons (summer and winter). Most hematological parameters were not adversely affected by land-treatment; however, platelet counts were 26% greater in cotton rats from land-treatment sites compared to reference sites in winter. Significant treatment-related differences were observed in total serum protein concentrations, organ mass and organ cellularity, but these differences were not consistent across the five land-treatment units. Lymphoproliferative responses of cotton rat splenocytes stimulated in vitro were elevated for a T-cell mitogen and depressed for a B-cell mitogen in animals from land-treatment compared to reference sites. The ability of splenocytes to proliferate in response to interleukin-2 receptor-binding was not influenced by treatment. Total yields of peritoneal cells, yield of peritoneal macrophages, and yield of peritoneal lymphocytes were influenced to varying degrees by land-treatment. Functionally, in vitro metabolic activity of peritoneal macrophages was 114% greater in cotton rats from land-treatment sites compared to reference sites during summer. These results indicate that petrochemical wastes applied to soils on these five land-treatment sites had variable immunomodulatory effects in resident cotton rats. Immune alterations for some assays were indicative of enhancement on some land-treatment sites while suppressive on other land-treatment sites, which could have been a function of type and concentration of immunotoxicants present on each site and highlights the uniqueness of each land-treatment site.     

Factors controlling the bioaccumulation of mercury and methylmercury by the estuarine amphipod Leptocheirus plumulosus

The bioaccumulation of inorganic mercury (HgI) and monomethylmercury (MMHg) by benthic organisms and subsequent trophic transfer couples the benthic and pelagic realms of aquatic systems and provides a mechanism for transfer of sedimentary contaminants to aquatic food chains. Experiments were performed to investigate the bioavailability and bioaccumulation of particle-associated HgI and MMHg by the estuarine amphipod Leptocheirus plumulosus to further understand the controls on bioaccumulation by benthic organisms. HgI and MMHg are particle reactive and have a strong affinity for organic matter, a potential food source for amphipods. Microcosm laboratory experiments were performed to determine the effects of organic matter on Hg bioaccumulation and to determine the major route of Hg uptake (i.e. sediment ingestion, uptake from water/porewater, or uptake from 'food'). Amphipods living in organic-rich sediment spiked with Hg accumulated less Hg than those living in sediments with a lower organic matter content. Feeding had a significant impact on the amount of HgI and MMHg accumulated. Similarly, amphipods living in water with little organic matter accumulated more Hg than those living in water with a greater percentage of organic matter. MMHg was more readily available for uptake than HgI. Experimental results, coupled with results from a bioaccumulation model, suggest that accumulation of HgI and MMHg from sediment cannot be accurately predicted based solely on the total Hg, or even the MMHg, concentration of the sediment, and sediment-based bioaccumulation factors. All routes of exposure need to be considered in determining the accumulation of HgI and MMHg from sediment to benthic invertebrates.     

PCDD/F inhibition by prior addition of urea to the solid fuel in laboratory experiments and results statistical evaluation

The objectives of this work were to study the effect of urea addition to the fuel before the combustion on the suppression of PCDD/F emissions, to examine the influence of urea to PCDD/F isomer patterns by employing statistical analysis techniques and to determine the most effective method of urea addition. Urea in the form of powder and as an aqueous solution was mixed with RDF and the fuel mixtures were incinerated in a lab-scale reactor at 1000 degrees C. PCDD/F emitted during combustion experiments were collected in a quartz wool filter downstream the reactor unit. Analysis and quantification of PCDD/F showed that urea significantly affected PCDD/F emissions. Combustion of RDF containing 10% w/w urea resulted in PCDD/F emissions lower than 8 I-TEQ ng/g RDF, while the corresponding average value from single RDF combustion was 17 I-TEQ ng/g RDF. The PCDD/F prevention capacity of urea was independent from the method of urea addition to the fuel, as similar results were obtained after the addition of urea in the solid and in the aqueous phases. Results assessment by statistical methods showed that isomer patterns remained almost stable and were not affected by the method of urea addition.     

Dimethylcarbonate for eco-friendly methylation reactions

Dimethylcarbonate (DMC), an environmentally friendly substitute for dimethylsulfate and methyl halides in methylation reactions, is a very selective reagent. Both under gas-liquid phase transfer catalysis (GL-PTC) and under batch conditions, with potassium carbonate as the catalyst, the reactions of DMC with methylene-active compounds (arylacetonitriles and arylacetoesters, aroxyacetonitriles and methyl aroxyacetates, benzylaryl- and alkylarylsulphones) produce monomethylated derivatives, with a selectivity not previously observed (i.e., >99%). The highly selective O-methylation of phenols and p-cresols by DMC is also attained by a new methodology using a continuous fed stirred tank reactor (CSTR) filled with a catalytic bed of polyethyleneglycol (PEG) and potassium carbonate.     

Guest dechlorination and covalent capture following photoexcitation of inclusion complexes in water

Photoexcitation of complexes between cyclophane 1 and 1- or 2-chloronaphthalene in aqueous solution leads to rapid dechlorination of the guest, a reaction driven by electron transfer from host to excited guest. The main photoproducts contain a naphthyl group covalently attached to the host framework. The results may lead to new approaches for remediating water contaminated with chlorinated aromatic compounds.     

Solar photocatalytic mineralization of commercial pesticides: acrinathrin

A comparative study of the degradation of commercial acrinathrin spiked in water using TiO2 photocatalysis and photolysis under sunlight was performed. Samples were analysed by liquid chromatography-diode array detector (HPLC-DAD) and gas chromatography-ion trap-mass spectrometric detector (GC-ITMS). Additional total organic carbon (TOC) analyses were carried out to evaluate the mineralisation rates. One photoproduct, 2-phenoxy benzaldehyde, was unequivocally identified and evaluated by GC-ITMS during the processes. Although acrinathrin is almost destroyed when exposed to irradiation for more than 400 h, photocatalysis with TiO2 noticeably reduced degradation to a few hours. In this case, with the additional presence of peroxydisulphate, in less than 2 h acrinathrin is completely destroyed. Mineralisation of acrinathrin, without catalyst, was only around 50% after 400 h of irradiation.