Re-evaluation of the conformational structure of sulfadiazine species using NMR and ab initio DFT studies and its implication on sorption and degradation

In the environment, the sorption and the degradation of organic pollutants are of increasing interest. The investigation of the chemical structures provides a basis for the development of a suitable binding model approach and for the mechanistic understanding of the chemical fate processes. The aim of this study was the identification of different species of the antibiotic compound sulfadiazine (SDZ) using (1)H and (13)C NMR experiments and ab initio density functional theory (DFT) calculations. In the neutral, aprotic solvent dimethylsulfoxide-d(6) (DMSO-d(6)), a new sulfadiazine structure containing an O-H-N hydrogen bond was identified. In the protic solvent water-d(2) and in dependence on pH and the position of the amidogen hydrogen atom nine possible SDZ conformations were analyzed and five structures were identified. Good conformity between theory and calculation of (1)H NMR was observed. Unfortunately, (13)C NMR is not sensitive enough for comparison and differentiation. In order to verify the identified structures, additional NBO/NLMO (natural localized molecular orbital) analyses were conducted (calculation of net atomic charges, bond polarity, atomic valence, and electron delocalization). Finally, conformation optimizations were performed in order to investigate the stability of the SDZ species. We showed that SDZ contains no S=O double bond, but that it has two S-O single bonds. Surprisingly, negative charges were observed at the pyrimidine nitrogen atom. With these results, the known structure of SDZ was revised. Studies of the geometrical structure and the torsion angles showed that SDZ is very flexible and can be easily fitted to the sorbent. These observations would explain the strong sorbance and hence the rapid formation of non-extractable residues in the environment because SDZ acts as a strong ligand. These results show that that the sulfonamide hydrogen is important for the biological activity but the pyrimidine nitrogen and the sulfonamide oxygen is responsible for the sorbance in environment.     

Organizational practices and workplace health and safety: A cross-sectional study in manufacturing companies

We report the results of a mail questionnaire for 312 manufacturing firms in the province of Ontario (Canada). We conducted a cross-sectional analysis of workplace level health and safety policies, practices and attitudes. Analyses were conducted across firm categories based upon lost-time frequency rate (LTFR) data. Lower LTFRs were associated with paternalistic initiatives, recording of occupational health and safety (OHS) measures, greater involvement of workers in decision-making, and better managerial attitudes concerning the importance of OHS. The composition of the Joint Health and Safety Committee (JHSC), a committee mandated in all workplaces we sampled, differed according to injury rate: the mean number of worker (vs. management) members on the JHSC was higher for lower injury sites, and the mean number of worker members attending JHSC meetings was also higher for lower injury worksites. In addition, workplaces with lower LTFR benefitted by having JHSCs with more executive functions and greater worker involvement. In conclusion, managerial and worker participation in OHS initiatives characterizes safer workplaces. Also, general concern of management towards OHS—illustrated by both attitudes and concrete actions—is also associated with lower injury rates.     

Policies towards proposals for large-scale natural resource projects: Attenuation versus postponement

The authors examine the problem of dealing with the environmental impact of uranium mining in Australia and consider its wider implications. Government, faced with unknown environmental and social damage from the initiation of uranium mining in northern Australia, has initiated an environmental impact assessment procedure. This requires the appellant company to provide information about the proposed project and its alternatives and is often followed by a period of ‘postponement’. This is compared with an alternative procedure, ‘attenuation’, allowing the project to proceed on a reduced scale in order to obtain information. Comparisons are made between the information which might be obtained by the two alternative procedures and the expected relative benefits and costs from a postponed project and an attenuated project.     

Study of the biodegradation of phenol in river water

As the disappearance of phenols from river water principally occurs by bacteriological degradation, the effect of varying several parameters, which can influence bacteriological activity and thus the degradation kinetics of phenol, was studied.In order to have an idea about what happens to phenol and its degradation products, we examined the degradation of ¹⁴C phenol.     

The effects of woodburning on the indoor residential air quality

Data from suburban residences in the Boston metropolitan area reveal a potential adverse impact on indoor air quality from woodburning in woodstoves and fireplaces. Ambient pollutant concentrations at each residence were compared to corresponding pollutant levels indoors at three locations (kitchen, bedroom, and activity room). Individual gaseous pollutant samples were averaged on an hourly basis while 24-h integrated samples of particulate matter were obtained. Ten gaseous pollutants were sampled along with total suspended particulates (TSP). Chemical analyses further determined ten components of TSP including trace metals, benzo-a-pyrene(B)aP, respirable suspended particulates (RSP), and water soluble sulfates and nitrates. Monitoring lasted two weeks at each residence and was conducted under occupied, real-life, conditions. Observed, elevated indoor concentrations of TSP, RSP, and BaP are attributed to woodburning. Data indicate that average indoor TSP concentrations during woodburning periods were about three times corresponding levels during nonwoodburning periods. The primary 24-h national ambient air quality standard (NAAQS) for TSP was exceeded once indoors during fireplace use, and the secondary, 24-h TSP NAAQS, was also exceeded indoors by RSP concentrations. Indoor BaP concentrations during woodstove use averaged five times more than during nonwoodburning periods. At this stage, results are only indicative, but the potential impact from elevated indoor concentrations of TSP, RSP, and BaP, attributed to woodburning, may have long-term health implications.     

AN ANALYSIS OF RISING IRRIGATION COSTS IN THE GREAT PLAINS1

ABSTRACT: Irrigation costs are rising rapidly on the 32 million acres irrigated with ground water. Ground water levels are declining under about 15 million of those acres adding to increased costs. However, from 1975 to 1982, 75 to 80 percent of increased ground water irrigation costs were due to higher nominal energy prices and interest rates. In real dollars, adjusted for inflation, these costs have risen faster than other irrigation costs and the real rise in commodity prices has been very small. A continuation of rapidly rising costs and slowly rising prices will shorten the economic life of those aquifers experiencing declining water levels. That same condition of prices and costs place all ground water irrigators in a disadvantaged position compared to nonirrigators and could cause a decline in ground water irrigation.     

Organochlorines and selenium in California night-heron and egret eggs

Exceptionally high concentrations of DDE were found in black-crowned night-heron (Nycticorax nycticorax) (geometric mean 8.62 g g^–1 wet wt.) and great egret (Casmerodius albus) (24.0 g g^–1) eggs collected from the Imperial Valley (Salton Sea), California in 1985. DDE concentrations in 14 of the 87 (16%) randomly selected night-heron eggs from six colonies (two in San Francisco Bay, three in the San Joaquin Valley, and one at Salton Sea) were higher than those associated with reduced reproductive success of night-herons (8 g g^–1). In addition, mean shell thickness of night-heron eggs collected from the San Joaquin Valley and from San Francisco Bay during 1982–1984 was significantly less than pre-DDT thickness and was negatively correlated (r=–0.50, n=75, P<0.0001) with DDE concentration. Mean selenium concentration in night-heron eggs from Salton Sea (1.10 g g^–1) was significantly higher than in eggs from three locations in the San Joaquin Valley, and in egret eggs from Salton Sea.     

Phytoremediation of dissolved phase organic compounds: Optimal site considerations relative to field case studies

The United States Environmental Protection Agency/Environmental Response Team (EPA/ERT) has been supporting and implementing the use of phytoremediation to remediate dissolved phase organic compounds at Superfund sites since March 1996. Since then, ERT has applied phytoremediation field plots, both pilot and full scale, to a variety of field conditions. These active sites vary considerably as to depth to groundwater, groundwater transmissivity, contaminant concentrations, contaminant hydrophobicity, climate, planting design, plant selection, planting technique, and type of monitoring. Here we compare the literature and discuss lessons learned at five Superfund sites. Current maintenance and monitoring techniques at these sites are also discussed with recommendations for the maintenance and monitoring of similar sites in the future. © 2003 Wiley Periodicals, Inc.     

CORRELATION OF SELECTED WELL WATER QUALITY PARAMETERS WITH SOIL AND AQUIFER HYDROLOGIC PROPERTIES1

ABSTRACT: The geographical distribution of well water specific electrical conductivity and nitrate levels in a 932 km² ground water quality study area in the Fresno-Clovis, California, indicated that frequently areas of lower ground water salinity were also areas of relatively greater soil and aquifer permeability. From these observations and certain assumptions we hypothesized that the quality of the well water should be better in areas with permeable soils and geological formations. Correlation and multiple linear regression analysis supported this hypothesis for well water salinity. However, well water nitrate levels were significantly negatively correlated with only the estimated equivalent specific yield of the aquifer system. The multiple R² values of the most significant multiple linear regression models showed that only a fourth to a third of the variability in well water specific electric conductivity and nitrate levels could be ascribed to the effects of the hydrogeological parameters considered with more than 90 percent confidence. This indicates that three-fourths to two-thirds of the variability in ground water salinity and nitrate levels may be related to land use. Thus, there is considerable room for land use management techniques to improve ground water quality and reduce its variability.     

INFLUENCE OF WELL WATER QUALITY VARIABILITY ON SAMPLING DECISIONS AND MONITORING1

ABSTRACT: Local governmental agencies responsible for decisions in ground water quality management need not only data on ground water quality but they also must understand the relationship of accuracies and risks associated with this data as related to the number of wells to sample. In this report we address this problem by using the philosophical doctrines of probabilism and relativism with simple statistical procedures. This requires a reasonable estimate of the population variance in a quality parameter for a given management-unit area, and requires that the decisionmaker formulate constraints with an acceptable standard error of the sample mean and be willing to accept some level of probability of being Wrong. This technique is illustrated using a 21-year data base of well water chemical data in a 653 km² ground water quality study area in the San Joaquin Valley of California.