Kinetic and structural relationships of transition monomeric and oligomeric carboxyl- and choline-esterases

The kinetic and structural relationships of eight electrophoretically pure mammalian serum and liver serine carboxylesterases (CE) and cholinesterases (ChE) have been studied. Eight CE's and ChE's, which were fully resolved but only partially purified, provided additional information. Five of the electrophoretically pure esterases were monomeric, and of these, four belonged to a new and widely distributed class. These four monomeric esterases hydrolyzed choline esters, but at widely differing rates. Thus two were termed monomeric butyrylcholinesterases, mBuChE I and II, and two were monomeric CE's (mCE). The rabbit liver mCE was not a subunit of the oligomeric CE (oCE), although the oCE also hydrolyzed choline esters at a very low rate. The complex kinetics of the mCE's, mBuChE's, oCE's, and of the oligomeric BuChE's of horse and human serum could be interpreted according to a single reaction scheme involving an allosteric site and the equation derived from it. Thus activation and inhibition at high substrate concentrations, together with sigmoidal activity versus substrate concentration plots, all of which characterize the reactions of these esterases, could be interpreted by a single scheme and equation. Structural and kinetic comparisons showed a progressive transition of properties from the oCE's through the mCE's to the oBuChE's. One of the purified mCE's was from horse serum, and it exhibited physical and kinetic properties unlike those of the liver mCE's or oCE's.     

Atmospheric concentrations of formic and acetic acid and related compounds in eastern and northern Austria

Formic and acetic acid were measured in the gas phase at three sites in eastern and northern Austria using an annular diffusion denuder sampling technique. The daytime background concentration of formic acid averaged 1.4 ±0.2 ppb (63 ± 9 nmol m⁻³) in a semirural area in eastern Austria. In a rural area in Austria the corresponding level was 0.9 ±0.3 ppb (40 ± 13 nmol m⁻³). About twice as high levels of formic acid were found during a photochemically active summer period and a wintertime pollution episode. The concentration of acetic acid was generally about 50 % lower than that of formic acid during daylight hours. In summer diurnal variation with a night-time minimum and a daytime maximum in the late afternoon hours was observed. The diurnal variation was not evident in results from measurements above the inversion layer or during winter conditions with snow cover. No increase in the formic and acetic acid levels was found in the airshed of Vienna, indicating that traffic emissions do not form a major primary source for the semirural concentrations measured. Although there might be biogenic sources for formic and acetic acid, our findings suggest a noticeable contribution from various anthropogenic emissions being a source for photochemical production of the acids.     

Dietary and environmental estrogens and antiestrogens and their possible role in human disease

Recent reports have suggested that dietary and environmental estrogens such as organochlorine pollutants may play a role in the increased incidence of breast cancer in women and disorders of the male reproductive tract. For example, elevated levels of DDE and polychlorinated biphenyls (PCB) have been measured in women with breast cancer. However, it should also be noted that numerous environmental and dietary compounds have also been characterized as antiestrogenic and as inhibitors of mammary cancer cell growthin vitro and/orin vivo. Some of these compounds include 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and related compounds, polynuclear aromatic hydrocarbons (PAH), other naturally-occurring TCDD receptor agonists, retinoids, phorbol esters, terpenes, fatty acids, and polysaccharides. Thus, it is possible that dietary and environmental estrogens and antiestrogens may be contra-active, and these interactions must be considered in the overall risk assessment of the potential adverse human and environmental health impacts of these chemicals.     

Patterns of PCDDs and PCDFs in human milk and food and their characterization by artificial neural networks

Artificial neural network (ANN) has been recently introduced as a tool for data analysis. In this study, Kohonen's self-organizing maps (SOMs), a special type of neural network, were applied to a set of PCDD/PCDF concentrations found in 54 human milk and 83 food samples, which were collected in a number of countries all over the world. Data were obtained from the scientific literature. The purpose of the study was to find a potential relationship between PCDD/PCDF congener profiles in human milk and the dietary habits of the different countries in which samples were collected. The comparison of the SOM component planes for human milk and foodstuffs indicates that those countries with a greater fish consumption show also higher PCDD/PCDF concentrations in human milk. SOMs enable both the visualization of sample units and the visualization of congener distribution.     

Modeling radium and radon transport through soil and vegetation

A one-dimensional flow and transport model was developed to describe the movement of two fluid phases, gas and water, within a porous medium and the transport of 226Ra and 222Rn within and between these two phases. Included in this model is the vegetative uptake of water and aqueous 226Ra and 222Rn that can be extracted from the soil via the transpiration stream. The mathematical model is formulated through a set of phase balance equations and a set of species balance equations. Mass exchange, sink terms and the dependence of physical properties upon phase composition couple the two sets of equations. Numerical solution of each set, with iteration between the sets, is carried out leading to a set-iterative compositional model. The Petrov-Galerkin finite element approach is used to allow for upstream weighting if required for a given simulation. Mass lumping improves solution convergence and stability behavior. The resulting numerical model was applied to four problems and was found to produce accurate, mass conservative solutions when compared to published experimental and numerical results and theoretical column experiments. Preliminary results suggest that the model can be used as an investigative tool to determine the feasibility of phytoremediating radium and radon-contaminated soil.     

Sorption and desorption of Cu and Cd by macroalgae and microalgae

The sorption and desorption of Cu and Cd by two species of brown macroalgae and five species of microalgae were studied. The two brown macroalgae, Laminaria japonica and Sargassum kjellmanianum, were found to have high capacities at pHs between 4.0 and 5.0 while for microalgae, optimum pH lay at 6.7. The presence of other cations in solution was found to reduce the sorption of the target cation, suggesting a competition for sorption sites on organisms. Sorption isotherms obeyed the Freundlich equation, suggesting involvement of a multiplicity of mechanisms and sorption sites. For the microalgae tested, Spirulina platensis had the highest capacity for Cd, followed by Nannochloropsis oculata, Phaeodactylum tricornutum, Platymonas cordifolia and Chaetoceros minutissimus. The reversibility of metal sorption by macroalgae was examined and the results show that both HCl and EDTA solutions were very effective in desorbing sorbed metal ions from macroalgae, with up to 99.5% of metals being recovered. The regenerated biomass showed undiminished sorption performance for the two metals studied, suggesting the potential of such material for use in water and wastewater treatment.     

Sources and fate of PCDD and PCDF

PCDD and PCDF were found in urban air particulates from St. Louis and Washington, D.C., and in sediments from the Great Lakes and Siskiwit Lake, Isle Royale. The similarity between the PCDD and PCDF found in air particulates and sediment samples and the presence of PCDD and PCDF in sediment from Siskiwit Lake (a location which can receive only atmospheric inputs) suggest that these compounds are emitted to the atmosphere from combustion sources. The historical input of PCDD and PCDF to dated sediment cores shows a strong increase since 1940, and this suggests that the incineration of chlorinated organic compounds is an important source of PCDD and PCDF to the environment.     

Agricultural work related injury and Ill-health and the economic cost

This paper contains a literature review of the occupational injuries and ill-health in agriculture world-wide and a survey of the attempts that have been made to estimate the resulting economic and social costs. Agricultural workers suffer a wide variety of disorders as a result of their occupation. These range from minor (cuts, bruises) to more severe (deep wounds, fractures), permanent (amputation, spinal cord injury) and fatal injury. Ill-health as a result of contact with animals, micro-organisms, plant material dusts or chemicals are associated with certain types of agriculture. There is an underlying but unquantified incidence of pain, stress and injury as a result of ergonomic problems due to poor working procedures and conditions. Statistics from many countries or regions show that agriculture consistently has one of the highest accident and injury rates of the industrial sectors. There are many causes for the work related injury and ill-health in agricultural workers. In developed countries, tractors and other machinery cause a significant proportion of the accidents and are a major cause of occupational deaths. In less developed countries, accidents due to hand tools such as hoes, sickles and cutting instruments are most prevalent. Animals are a significant cause of injury and ill-health in many countries. Debilitating allergic reactions in the respiratory tract or the skin are caused by exposures to organic dusts, or by contact with allergenic plants in the field respectively. Where comparative data are available, occupational pesticide poisoning in agriculture is a small proportion (< 1–4%) of the total work related disorders. Because of the wide variety of occupational risks to agricultural workers, it is emphasised that if one type of agricultural practice is replaced by another then the risks from the alternative procedure need to be considered. If, for example, agrochemical pest control practices are replaced by methods involving the increased use of machinery, draught animals or manual operations, then an assessment of the resulting risks should be taken into account. Some of the economic costs of occupational injury and ill-health in agriculture can be quantified directly, such as medical costs, the cost of rehabilitation and loss of earnings. Other costs are more difficult to estimate such as loss of opportunity and income foregone for permanent and fatal injury and for the effect on a victim’s family. The estimation of the overall economic costs to farming communities and national agriculture requires further development. When one agricultural practice is replaced wholly or partly by another, for example agrochemical pest control by alternative control methods, then it is necessary to take into account the occupational health costs of the alternative procedure for realistic comparative assessment. There are a number of issues which require continued or increased attention by the relevant national and international authorities and by the agricultural industry. These include the improved collection and collation of occupational health statistics, a better understanding of the extent of ergonomic problems in agriculture, more realistic assessments of the cost of occupational injury and ill-health and the continued need to reduce occupational health disorders by appropriate training and education in agricultural practices and the use of agricultural equipment.     

Modelling PAHs adsorption and sequestration in freshwater and marine sediments

Chemical sequestration is a natural process taking place in sediments and soils which reduces the availability of hydrophobic compounds such as polycyclic aromatic hydrocarbons (PAHs). The rate of sequestration following the release of PAHs into the aquatic environment is still unexplored. To measure kinetic parameters and investigate governing factors of adsorption and sequestration of individual PAHs, natural sediment slurries were spiked with [2H]-PAHs and periodically extracted with a high molecular weight surfactant solution to determine changes in the available fraction over periods of 7-28 days. Dissolved and/or colloidal [2H]-PAHs were first adsorbed on particles within 4-7 days. Adsorbed molecules became slowly sequestered into sediment particles and were gradually more difficult to extract over a period of 17-20 days. An empirical model based on a three-compartment dynamic system was developed to quantify the sequestration rate constants of a group of seven selected PAHs. The sequestration process was assumed to be a first-order consecutive and irreversible two-stage reaction. The model was tested with lowly contaminated marine sediment and moderately contaminated freshwater sediment. Adsorption rate constants ranged between 0.056 h(-1) and 0.017 h(-1) and were approximately ten times higher than sequestration rate constants. Light PAHs were faster to enter into the sequestration process whereas colloidal dispersion of heavier less soluble PAHs reduced their adsorption rates. Although quite simple, this model was efficient to compute kinetic parameters for most PAHs studied and predict that only a small proportion of adsorbed PAHs would remain extractable after one month.     

Bacterial and archaeal diversity in oil fields and reservoirs and their potential role in hydrocarbon recovery and bioprospecting

Environmental Science and Pollution Research - Hydrocarbon is a primary source of energy in the current urbanized society. Considering the increasing demand, worldwide oil productions are declining...     

Particulate and Nicotine Sampling in Public Facilities and Offices

Abstract

The purpose of this study was to characterize and measure indoor air quality in public facilities and office buildings. The pollutants of interest were particulate matter smaller than 2.5 μm in diameter, PM-2.5, and environmental tobacco smoke (ETS). Integrated PM- 2.5 samples were taken on Teflon membrane filters using Harvard Aerosol Impactors as a pre-size selector. Filters were analyzed by gravimetric analysis. Nicotine, which was used as a marker for ETS, was collected on sodium-bisulfate-impregnated, glass-fiber filters and was analyzed by gas chromatography. Twenty-one structures were monitored in Metropolitan Boston. Measured particle concentrations ranged from 6.0 μg/m³ to about 550 μg/m³. Nicotine concentrations were as high as 26 μg/m³ in a designated smoking room. Real-time measurements were also taken using two types of nephelometers; a Handheld Aerosol Monitor (HAM) and a Miniature Real-Time Aerosol Monitor (MINIRAM). Short-term field measurements with these instruments correlated better with the integrated PM-2.5 concentrations in smoking locations than with concentrations in non-smoking areas.     

Mercury and selenium in wild and experimental seals

This paper describes the tissue distribution of inorganic mercury, organic mercury and selenium in Dutch and British seals as well as in seals which were dosed with methylmercury under experimental conditions.In the experimental animals, a time-related increase of both mercury and selenium was found in liver and kidney after the administration of methylmercury, while in the other tissues examined, e.g. brain, thyroid, blood, only the concentrations of mercury increased.In the wild seals, it was also demonstrated that the selenium concentrations showed a positive correlation with the concentrations of mercury.Atomic ratios of mercury and selenium were close to one in the wild seals as was also found in previous studies. However, atomic ratios above one were found in seals fed additional methylmercury.In vitro studies with liver homogenates of seals did not provide evidence for the presence of a biochemical demethylation mechanism nor for any effect of selenium on the demethylation process.     

Phosphorus Flows to and from Swedish Agriculture and Food Chain

Phosphorus flows in Swedish agriculture and food chain were studied by material flow analysis. The system studied included agriculture, food consumption, related waste and wastewater from private households and municipal wastewater treatment plants. Swedish farmland had net annual phosphorus inputs of ~12 600 metric tons (4.1 kg P ha⁻¹) in 2008–2010. The total import of phosphorus in food and feed to Sweden exceed imports of phosphorus in fertilizers. Despite strict animal density regulations relating to manure phosphorus content, phosphorus is accumulating on Swedish animal farms. The total quantity of manure produced greatly exceeds imported mineral phosphorus fertilizer and almost equals total phosphorus inputs to Swedish farmland.     

Ozone and grosswetterlagen

Meteorological conditions have a decisive impact on surface ozone concentrations. In this study, an empirical model is used to explain the interdependence of ozone and grosswetterlagen. Different meteorological parameters such as air temperature, global solar radiation, relative humidity, wind direction and wind speed are used. Additional nitric oxide (NO) was taken as a representative for the emission situation and ozone maximum of the preceding day in order to evaluate the development of the photochemical situation. The dataset includes data collected over a period of three years (1992–1994) from three stations outside of Munich and one in the center of Munich. All values become variables by calculating means, sums or maxima of the basic dataset consisting of half-hour means. Seasonal periodicity of data is detected with Fourier analysis and eliminated by a division method after computing a seasonal index. The dataset is divided into three different grosswetterlagen groups, depending on main wind direction. One mostly cyclonic (westerly winds), onemixed (alternating winds) and one onlyanticyclonic (easterly winds). The last is completed with one summertime group including values from April to August. Factor analysis is performed for each group to obtain independent linear variable combinations. Overall, relative humidity is the dominant parameter, a typical value indicating meteorological conditions during a grosswetterlage. Linear multiple regression analysis is performed using the factors obtained to reveal how the ozone concentrations are explained in terms of meteorological parameters and NO. The results improve from cyclonic to anticyclonic grosswetterlagen in conformance with the increasing significance of photochemistry, indicated by the high solar radiation and high temperature, and the low relative humidity and low wind speed. The explained variance r² reaches its maximum with more than 50 % of the time in Munich center. This empirical model is applicable to the forecasting of local ozone maximum concentrations with a total standard error deviation of 8.5 to 12.8 % and, if ozone concentrations exceed 80 ppb, with a standard error deviation of 5.4 to 9.5 %.     

Ozone and grosswetterlagen

Meteorological conditions have a decisive impact on surface ozone concentrations. In this study, an empirical model is used to explain the interdependence of ozone and grosswetterlagen. Different meteorological parameters such as air temperature, global solar radiation, relative humidity, wind direction and wind speed are used. Additional nitric oxide (NO) was taken as a representative for the emission situation and ozone maximum of the preceding day in order to evaluate the development of the photochemical situation. The dataset includes data collected over a period of three years (1992–1994) from three stations outside of Munich and one in the center of Munich. All values become variables by calculating means, sums or maxima of the basic dataset consisting of half-hour means. Seasonal periodicity of data is detected with Fourier analysis and eliminated by a division method after computing a seasonal index. The dataset is divided into three different grosswetterlagen groups, depending on main wind direction. One mostly cyclonic (westerly winds), one mixed (alternating winds) and one only anticyclonic (easterly winds). The last is completed with one summertime group including values from April to August. Factor analysis is performed for each group to obtain independent linear variable combinations. Overall, relative humidity is the dominant parameter, a typical value indicating meteorological conditions during a grosswetterlage. Linear multiple regression analysis is performed using the factors obtained to reveal how the ozone concentrations are explained in terms of meteorological parameters and NO. The results improve from cyclonic to anticyclonic grosswetterlagen in conformance with the increasing significance of photochemistry, indicated by the high solar radiation and high temperature, and the low relative humidity and low wind speed. The explained variance r² reaches its maximum with more than 50 % of the time in Munich center. This empirical model is applicable to the forecasting of local ozone maximum concentrations with a total standard error deviation of 8.5 to 12.8 % and, if ozone concentrations exceed 80 ppb, with a standard error deviation of 5.4 to 9.5 %.     

Quantification of carbamazepine and atrazine and screening of suspect organic contaminants in surface and drinking waters

A new approach for the identification of suspect trace organic contaminants in drinking and surface waters is presented. Samples were initially analyzed using a target determination method for two contamination tracers, carbamazepine (CBZ) and atrazine (ATZ). This method used offline solid-phase extraction and online solid-phase extraction techniques coupled to liquid chromatography-triple quadrupole mass spectrometry to accelerate the sample preparation process and improve method performance. CBZ and ATZ were found respectively in 31% and 56% of the samples, and concentrations were usually <20 ng L⁻¹. These samples were re-analyzed with a similar method on a quadrupole time-of-flight mass spectrometer to identify suspect contaminants by means of exact mass measurements and isotope patterns. A database of 264 common organic contaminants was built and used in conjunction with a Molecular Feature algorithm to identify the presence of these substances in drinking and surface water collected from different sources at various locations across Canada. Several organic contaminants were identified in the samples, but only the presence of caffeine, desethylatrazine, simazine and venlafaxine could be verified by comparison to pure standards. The presence of desethylatrazine was also confirmed by MS/MS experiments. These results suggest that target analysis for tracers of organic contamination may be a helpful tool to prioritize samples which should be further screened for suspect contaminants. This study also shows that the combination of separation techniques (offline and online SPE, LC) contribute to advance the applicability of high-resolution mass spectrometry for the identification of trace organic contaminants by accelerating the preparation step, reducing complexity and increasing analyte concentrations for optimal detection.     

Prenatal and postnatal exposure to diazinon and its effect on spermatogram and pituitary gonadal hormones in male offspring of rats at puberty and adulthood

The objective of this research is to study the possible reproductive adverse effects of diazinon on rat offspring exposed in utero and during lactation. Twenty-four Sprague–Dawley female rats (10–12 week old) were randomly assigned to four groups, each consisting of six rats. Group 1 served as the control and these rats were given normal saline orally. Rats in groups 2, 3, and 4 were administered diazinon, dissolved in saline at 10, 15, 30 mg/ kg^?1 body weight, per oral, once daily, during mating, pregnancy and lactation. The male offsprings were examined at puberty and adulthood for body weight, testis weight, epididymis weight, sperm count, motility and morphology, pituitary-gonadal hormone levels. At 30 mg kg^?1 dose, the male offsprings showed a decrease in testicular weight, sperm count, motility, with an increase in abnormal sperm percentage and a decline in pituitary-gonadal hormones, at puberty. Upon attaining adulthood, there was a decrease in testicular weight, sperm count and motility with an increase in abnormal sperm percentage and a decrease in pituitary hormone level. There was evidence of some adverse reproductive effects on the male offspring at the 15 mg/ kg^?1 dose. Most of the adverse effects were irreversible and were evident at both puberty and adulthood in the offsprings, although a few parameters reverted to the normal growth pattern. Diazinon is a reproductive toxicant for male offsprings if exposed during prenatal and postnatal phases.     

Mobility of metals and metalloids from SHOS coal ash and slag deposit: mineralogical and geochemical constraints

Environmental Science and Pollution Research - Deposits remained after coal combustion are a well-known occurrence in the world; unfortunately, only a small percentage of such deposits are...     

Integrated planning and spatial evaluation of megasite remediation and reuse options

Redevelopment of large contaminated brownfields (megasites) is often hampered by a lack of communication and harmonization among diverse stakeholders with potentially conflicting interests. Decision support is required to provide integrative yet transparent evaluation of often complex spatial information to stakeholders with different areas of expertise. It is considered crucial for successful redevelopment to identify a shared vision of how the respective contaminated site could be remediated and redeveloped. We describe a framework of assessment methods and models that analyzes and visualizes site- and land use-specific spatial information at the screening level, with the aim to support the derivation of recommendable land use layouts and to initiate further and more detailed planning. The framework integrates a GIS-based identification of areas to be remediated, an estimation of associated clean-up costs, a spatially explicit market value appraisal, and an assessment of the planned future land use's contribution to sustainable urban and regional development. Case study results show that derived options are potentially favorable in both a sustainability and an economic sense and that iterative re-planning is facilitated by the evaluation and visualization of economic, ecological and socio-economic aspects. The framework supports an efficient early judgment about whether and how abandoned land may be assigned a sustainable and marketable land use.     

Air Pollution and Mortality: Issues and Uncertainties

Abstract

Results from 31 epidemiology studies linking air pollution with premature mortality are compared and synthesized. Consistent positive associations between mortality and various measures of air pollution have been shown within each of two fundamentally different types of regression studies and in many variations within these basic types; this is extremely unlikely to have occurred by chance. In this paper, the measure of risk used is the elasticity, which is a dimensionless regression coefficient defined as the percentage change in the dependent variable associated with a 1% change in an independent variable, evaluated at the means. This metric has the advantage of independence from measurement units and averaging times, and is thus suitable for comparisons within and between studies involving different pollutants. Two basic types of studies are considered: time-series studies involving daily perturbations, and cross-sectional studies involving longer-term spatial gradients. The latter include prospective studies of differences in individual survival rates in different locations and studies of the differences in annual mortality rates for various communities.

For a given data set, time-series regression results will vary according to the seasonal adjustment method used, the covariates included, and the lag structure assumed. The results from both types of cross-sectional regressions are highly dependent on the methods used to control for socioeconomic and personal lifestyle factors and on data quality. Amajor issue for all of these studies is that of partitioning the response among collinear pollution and weather variables. Previous studies showed that the variable with the least exposure measurement error may be favored in multiple regressions; assigning precise numerical results to a single pollutant is not possible under these circumstances. We found that the mean overall elasticity as obtained from timeseries studies for mortality with respect to various air pollutants entered jointly was about 0.048, with a range from 0.01 to 0.12. This implies that about 5% of daily mortality is associated with air pollution, on average. The corresponding values from population-based cross-sectional studies were similar in magnitude, but the results from the three recent prospective studies varied from zero to about five times as much. Long-term responses in excess of short-term responses might be interpreted as showing the existence of chronic effects, but the uncertainties inherent in both types of studies make such an interpretation problematic.