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.     

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.     

Semiconductor-assisted photocatalytic degradation of reactive dyes in aqueous solution

This work reports the semiconductor-assisted photochemical degradation of reactive dyes. In an oxygenated-UV-ZnO system almost total decolorization of Remazol Brilliant Blue R, Remazol Black B, Reactive Blue 221 and Reactive Blue 222 was observed in reaction times of about 60 min. Extending the photochemical treatment up to 120 min, mineralization higher than 80% for all the dyes was observed. During the same period, the residual acute toxicity was significantly reduced only for Remazol Black B. A systematic optimization study carried out by factorial design showed that for the reactive dyes tested, the ZnO semiconductor exhibits a better efficiency than that observed with anatase TiO2. A synergistic effect in the coupled TiO2-ZnO system was not observed.     

An intelligent emissions controller for fuel lean gas reburn in coal-fired power plants

The application of artificial intelligence techniques for performance optimization of the fuel lean gas reburn (FLGR) system is investigated. A multilayer, feedforward artificial neural network is applied to model static nonlinear relationships between the distribution of injected natural gas into the upper region of the furnace of a coal-fired boiler and the corresponding oxides of nitrogen (NOx) emissions exiting the furnace. Based on this model, optimal distributions of injected gas are determined such that the largest NOx reduction is achieved for each value of total injected gas. This optimization is accomplished through the development of a new optimization method based on neural networks. This new optimal control algorithm, which can be used as an alternative generic tool for solving multidimensional nonlinear constrained optimization problems, is described and its results are successfully validated against an off-the-shelf tool for solving mathematical programming problems. Encouraging results obtained using plant data from one of Commonwealth Edison's coal-fired electric power plants demonstrate the feasibility of the overall approach. Preliminary results show that the use of this intelligent controller will also enable the determination of the most cost-effective operating conditions of the FLGR system by considering, along with the optimal distribution of the injected gas, the cost differential between natural gas and coal and the open-market price of NOx emission credits. Further study, however, is necessary, including the construction of a more comprehensive database, needed to develop high-fidelity process models and to add carbon monoxide (CO) emissions to the model of the gas reburn system.     

The deep-sea as a final global sink of semivolatile persistent organic pollutants? Part I: PCBs in surface and deep-sea dwelling fish of the north and south Atlantic and the Monterey Bay Canyon (California)

The understanding of the global environmental multiphase distribution of persistent organic pollutants (POPs) as a result of the physico-chemical properties of the respective compounds is well established. We have analysed the results of a vertical transport of POPs from upper water layers (0-200 m) to the deepwater region (> 800 m) in terms of the contamination of the biophase in both water layers. The contents of persistent organochlorine compounds like polychlorinated biphenyls (PCBs) in fish living in the upper water layers of the North Atlantic and the South Atlantic, and at the continental shelf of California (Marine Sanctuary Monterey Bay and its deep-sea Canyon) are compared to the levels in deep-sea or bottom dwelling fish within the same geographic area. The deep-sea biota show significantly higher burdens as compared to surface-living species of the same region. There are also indications for recycling processes of POPs--in this case the PCBs--in the biophase of the abyss as well. It can be concluded that the bio- and geo phase of the deep-sea may act similarly as the upper horizons of forest and grasslands on the continents as an ultimate global sink for POPs in the marine environment.     

Interpreting the relationship between pheromone component emission from commercial lures and captures of Helicoverpa zea (Boddie) in bucket and cone traps

Male corn earworm moths, Helicoverpa zea (Boddie), were captured in conical Texas pheromone traps (cone traps) and bucket traps baited with four different commercial lures manufactured by three different manufacturers. Because significant numbers were captured in bucket traps baited with some of the lures, and none with others, the volatile emissions from all of the lures were sampled and analyzed by gas chromatographic methods. The numbers of males captured in two types of trap were compared with bait emissions in an endeavor to define a more effective lure for bucket traps. The lure from one manufacturer captured the same numbers of males in both trap types; one captured more in bucket traps than in cone traps, and another captured only a small number in bucket traps. The emission rate of all active compounds from each of the different lures was approximately linear for the duration of the assays. A gas-liquid chromatographic peak associated with a third compound, (Z)-9-tetradecenal, which reduces behavioral responses, was observed in the emissions from all lures evaluated. The effectiveness of the Hercon (Emmigsville, PA) lure in capturing males in both types of trap was associated with a lower emission of (Z)-11-hexadecenal, (Z)-9-hexadecenal and (Z)-9-tetradecenal than from the other lures.