Microbial degradation of phthalic acid esters under anaerobic digestion of sludge

The microbial degradation by anaerobic sludge of three phthalates, priority pollutants, listed by both China National Environmental Monitoring Center and the U.S.EPA, namely, dimethyl (DMP), di-n-butyl (DBP) and di-n-octyl (DOP) phthalates was investigated. The experimental results indicated that the biodegradation rate and the biodegradability of three phthalates under anaerobic conditions appeared to be related to the length of the alkyl-side chains. More than 90% of DMP and DBP with the short alkyl-side chain phthalates can be degraded, whereas the DOP degradation appeared to be relatively slow under the same experimental conditions. The quantity of methane produced was measured and the results showed that both the ester groups and the phthalate ring were mineralized at a significant rate. The kinetics study demonstrated that the biodegradation of three phthalates conformed to the first-order model with respect to their concentrations.     

Estimating separately personal exposure to ambient and nonambient particulate matter for epidemiology and risk assessment: why and how

This paper discusses the legal and scientific reasons for separating personal exposure to PM into ambient and nonambient components. It then demonstrates by several examples how well-established models and data typically obtained in exposure field studies can be used to estimate both individual and community average exposure to ambient-generated PM (ambient PM outdoors plus ambient PM that has infiltrated indoors), indoor-generated PM, and personal activity PM. Ambient concentrations are not highly correlated with personal exposure to nonambient PM or total PM but are highly correlated with personal exposure to ambient-generated PM. Therefore, ambient concentrations may be used in epidemiology as an appropriate surrogate for personal exposure to ambient-generated PM. Suggestions are offered as to how exposure to ambient-generated PM may be obtained and used in epidemiology and risk assessment.     

Monitoring, modelling and environmental exposure assessment of industrial chemicals in the aquatic environment

Monitoring and laboratory data play integral roles alongside fate and exposure models in comprehensive risk assessments. The principle in the European Union Technical Guidance Documents for risk assessment is that measured data may take precedence over model results but only after they are judged to be of adequate reliability and to be representative of the particular environmental compartments to which they are applied. In practice, laboratory and field data are used to provide parameters for the models, while monitoring data are used to validate the models' predictions. Thus, comprehensive risk assessments require the integration of laboratory and monitoring data with the model predictions. However, this interplay is often overlooked. Discrepancies between the results of models and monitoring should be investigated in terms of the representativeness of both. Certainly, in the context of the EU risk assessment of existing chemicals, the specific requirements for monitoring data have not been adequately addressed. The resources required for environmental monitoring, both in terms of manpower and equipment, can be very significant. The design of monitoring programmes to optimise the use of resources and the use of models as a cost-effective alternative are increasing in importance. Generic considerations and criteria for the design of new monitoring programmes to generate representative quality data for the aquatic compartment are outlined and the criteria for the use of existing data are discussed. In particular, there is a need to improve the accessibility to data sets, to standardise the data sets, to promote communication and harmonisation of programmes and to incorporate the flexibility to change monitoring protocols to amend the chemicals under investigation in line with changing needs and priorities.     

Determination of Q1, an unknown organochlorine contaminant, in human milk, Antarctic air, and further environmental samples

Q1, an organochlorine component with the molecular formula C(9)H(3)Cl(7)N(2) and of unknown origin was recently identified in seal blubber samples from the Namibian coast (southwest of Africa) and the Antarctic. In these samples, Q1 was more abundant than PCBs and on the level of DDT residues. Furthermore, Q1 was more abundant in seals from the Antarctic than the Arctic. To prove this assumption, gas chromatography-electron-capture negative ion mass spectrometry (GC/ECNI-MS), which is sensitive and selective for Q1, allowed for screening of traces of Q1 even in samples with particularly high levels of other organochlorine contaminants. Q1 was isolated by high-performance liquid chromatography (HPLC) from a skua liver sample. A 1:1 mixture with trans-nonachlor in electron-capture detectors (ECDs) was used to determine the relative response factor with ECNI-MS. The ECNI-MS response of Q1 turned out to be 4.5 times higher than that of trans-nonachlor in an ECD. With GC/ECNI-MS in the selected ion-monitoring mode, four Antarctic and four Arctic air samples were investigated for the presence of Q1. In the Antarctic air samples, Q1 levels ranged from 0.7 to 0.9 fg/m(3). In Arctic air samples, however, Q1 was below the detection limit (<0.06 fg/m(3) or 60 ag/m(3)). We also report on high Q1 levels in selected human milk samples (12-230 microg/kg lipid) and, therefore, suggested that the unknown Q1 is an environmental compound whose origin and distribution should be investigated in detail. Our data confirm that Q1 is a bioaccumulative natural organochlorine product. Detection of a highly chlorinated natural organochlorine compound in air and human milk is novel.     

Seedling insensitivity to ozone for three conifer species native to Great Smoky Mountains National Park

Field symptoms typical of ozone injury have been observed on several conifer species in Great Smoky Mountains National Park, and tropospheric ozone levels in the Park can be high, suggesting that ozone may be causing growth impairment of these plants. The objective of this research was to test the ozone sensitivity of selected conifer species under controlled exposure conditions. Seedlings of three species of conifers, Table Mountain pine (Pinus pungens), Virginia pine (Pinus virginiana), and eastern hemlock (Tsuga canadensis), were exposed to various levels of ozone in open-top chambers for one to three seasons in Great Smoky Mountains National Park in Tennessee, USA. A combination of episodic profiles (1988) and modified ambient exposure regimes (1989-92) were used. Episodic profiles simulated an average 7-day period from a monitoring station in the Park. Treatments used in 1988 were: charcoal-filtered (CF), 1.0x ambient, 2.0x ambient, and ambient air-no chamber (AA). In 1989 a 1.5x ambient treatment was added, and in 1990, additional chambers were made available, allowing a 0.5x ambient treatment to be added. Height, diameter, and foliar injury were measured most years. Exposures were 3 years for Table Mountain pine (1988-90), 3 years for hemlock (1989-91), and 1 and 2 years for three different sets of Virginia pine (1990, 1990-91, and 1992). There were no significant (p<0.05) effects of ozone on any biomass fraction for any of the species, except for older needles in Table Mountain and Virginia pine, which decreased with ozone exposure. There were also no changes in biomass allocation patterns among species due to ozone exposure, except for Virginia pine in 1990, which showed an increase in the root:shoot ratio. There was foliar injury (chlorotic mottling) in the higher two treatments (1.0x and 2.0x for Table Mountain and 2.0x for Virginia pine), but high plant-to-plant variability obscured formal statistical significance in many cases. We conclude, at least for growth in the short-term, that seedlings of these three conifer species are insensitive to ambient and elevated levels of ozone, and that current levels of ozone in the Park are probably having minimal impacts on these particular species.     

Trace elements, organochlorines, polycyclic aromatic hydrocarbons, dioxins, and furans in lesser scaup wintering on the Indiana Harbor Canal

During the winter of 1993-94, male lesser scaup (Aythya affinis) were collected on the heavily polluted Indiana Harbor Canal (IHC), East Chicago, IN, USA, and examined for tissue contaminant levels. Lesser scaup collected on the IHC had higher concentrations of cadmium (Cd), mercury (Hg), selenium (Se), polychlorinated biphenyls (PCBs), selected organchlorine pesticides, polychlorinated dibenzodioxins, polychlorinated dibenzofurans, polycyclic aromatic hydrocarbons, and aliphatic hydrocarbons than reference birds. Of the scaup collected on the IHC, 44% had Cd concentrations in the liver considered above background for freshwater waterfowl (>3 microg/g dry wt.), 50% had Se concentrations in the liver above a level possibly harmful to the health of young and adult birds (>33 microg/g dry wt.), and 88% of the scaup carcasses exceeded the PCB human consumption guidelines for edible poultry in the USA (>3.0 microg/g lipid wt.). The ratio of pristane:n-heptadecane concentrations in 47% of lesser scaup collected on IHC was elevated above 1.0, which is indicative of chronic exposure to petroleum hydrocarbons.     

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.     

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.     

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.