Photodegradation of sulfonamides and their N 4-acetylated metabolites in water by simulated sunlight irradiation: kinetics and identification of photoproducts

Once released into the aquatic environment, pharmaceuticals may undergo different degradation processes. Photodegradation, for example, might be an important elimination process for light-sensitive pharmaceuticals, such as antibiotics. In this study, the fate of sulfonamides (sulfamethazine, sulfadiazine, and sulfamethoxazole) and their N ⁴-acetylated metabolites (N ⁴-acetylsulfadiazine, N ⁴-acetylsulfamethazine, and N ⁴-acetylsulfamethoxazole) under simulated sunlight irradiation was investigated. The irradiation resulted in total or almost total degradation (88 to 98 %) of the pharmaceuticals tested, except for sulfamethazine (52 %), during 24 h of irradiation. The photoproducts of all investigated pharmaceuticals have been analyzed using high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry. Structure elucidation performed from photodegradation products of both, sulfonamides and their N ⁴-acetylated metabolites, clearly showed two major formation pathways. These were cleavage of the sulfonamide bond as well as SO₂ extrusion. In total, nine photoproducts were elucidated. Among these photoproducts, the tautomers of sulfamethoxazole and desulfonated products of sulfadiazine and sulfamethazine were also present. Tautomers of sulfadiazine and sulfamethazine have been characterized here for the first time as well as some photoproducts of sulfadiazine, sulfametoxazole, and their metabolites N ⁴-acetylsulfadiazine and N ⁴-acetylsulfametoxazole. The obtained results are an important piece in the complex puzzle for assessing the environmental fate of sulfonamides and their metabolites in the environment.     

Trends of perfluorochemicals in Greenland ringed seals and polar bears: Indications of shifts to decreasing trends

Time-series of perfluorinated alkylated substances (PFASs) in East Greenland polar bears and East and West Greenland ringed seals were updated in order to deduce whether a response to the major reduction in perfluoroalkyl production in the early 2000s had occurred. Previous studies had documented an exponential increase of perfluorooctane sulphonate (PFOS) in liver tissue from both species. In the present study, PFOS was still the far most dominant compound constituting 92% (West Greenland ringed seals), 88% (East Greenland ringed seals) and 85% (East Greenland polar bears). The PFOS concentrations increased up to 2006 with doubling times of approximately 6 years for the ringed seal populations and 14 years in case of polar bears. Since then a rapid decrease has occurred with clearing half-lives of approximately 1, 2 and 4 years, respectively. In polar bears perfluorohexane sulphonate (PFHxS) and perfluorooctane sulphonamide (PFOSA) also showed decreasing trends in recent years as do perfluorodecanoic acid (PFDA) and perfluoroundecanoic acid (PFUnA). For the West Greenland ringed seal population perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), PFDA and PFUnA peaked in the mid 2000s, whereas PFNA, PFDA and PFUnA in the East Greenland population have been stable or increasing in recent years. The peak of PFASs in Greenland ringed seals and polar bears occurred at a later time than in Canadian seals and polar bears and considerably later than observed in seal species from more southern latitudes. We suggest that this could be explained by the distance to emission hot-spots and differences in long-range transport to the Arctic.     

Review of Recent Studies of Sulfur Oxides as Air Pollutants

The current literature on the role of sulfur dioxide in air pollution     

Limitations of the Lead Acetate Impregnated Paper Tape Method for Hydrogen Sulfide

Field experience with the lead acetate impregnated paper tape sampler has indicated that large errors may arise in this method due to fading of the color of the precipitated lead sulfide spots. This fading is due to the action of light, sulfur dioxide, ozone, on other substances capable of oxidizing lead sulfide. The moisture content or relative humidity of the air sample must be maintained at an appropriate level to ensure reaction with the impregnated paper tape. The effects of the factors have been investigated in laboratory experiments with known concentrations of H₂S. A number of antioxidants were studied in relation to the stability of the resultant spots to light and oxidation Orthophenyl phenol was found to be the most effective antioxidant for this purpose. A number of necessary precautions to be employed in the use of the lead acetate method are recommended and the limitations are discussed.     

Roof Monitor Emissions: Test Methodology

Studies of roof monitor emissions are conducted for two reasons: (1) to obtain design data necessary to engineer control systems to meet existing regulations, and (2) to determine projected control costs which can influence present day proposals for process change. Heated wire anemometers and rotating vane anemometers have been selected for velocity measurements, and high-volume air samplers have been selected to collect the particulate sample. Evaluation of other types of velocity sensing devices are described in the paper.

Roof monitor studies must be preceded by a preliminary survey to allow the project engineer to determine the test sampling locations and specific methodology necessary for the given study, and to allow the engineer to determine the type of safety equipment, scaffolds, and power requirements necessary to complete the study.

Field tests are conducted by operating a number of high-volume air samplers simultaneously while at the same time measuring the velocity of the gas through the monitor opening. Curves of particulate concentration and velocity as a function of monitor length are constructed. The concentration and velocity curves are then integrated together and the resultant curve is multiplied by the monitor width to determine a curve of mass emission rate as a function of monitor length. The total mass emission rate is represented by the area under the mass emission rate curve.

Procedures for calibrating the anemometers and correcting for the effect of power fluctuation on the high-volume sampler operation are described. Data evaluation procedures and discussion of test error are also described.

A study can cost between 10 and 20 thousand dollars, including the cost of manpower and the cost of scaffolds, power, cables, etc. It can take four months or more to conduct a study, from the preliminary survey phase through the report phase.     

Applicability of the Mass Concentration Standards for Particulate Matter in Alaskan Areas

The so-called “Six Month Study” of the air toxics problem in the United States was initiated in November 1983 by the U.S. Environmental Protection Agency. The study focused on the magnitude, nature, and distribution of the problem—three major issues that were felt to be most useful to policy makers as they attempted to define the scope and direction of a national program for controlling toxic air pollutants. The following paper is based on a draft staff report on the study released for review in September 1984. The report has not been formally released by the U.S. EPA; a final report is due by late spring of 1985.     

interpretation of air quality data with respect to the national ambient air quality standards

San Diego Gas &; Electric has developed a quality assurance program for continuous emission monitors (CEM). Extractive, rather than in situ, monitors were selected as a result of an in-house evaluation program. Two extractive systems have been certified and a good operating and maintenance record has been established on these systems. A successful program requires the involvement and support of all affected personnel. It is desirable to have one or two key personnel coordinate the development of the program. It is also highly desirable to have good in-house source testing capabilities.     

The Need for Representative Ambient Air Carbon Monoxide Sampling

Recent investigations have indicated that ambient air CO measurements may not reflect population exposure to CO. The lack of correlation may be due to improper siting of CO instruments, improper interpretation of air quality data, or both. Studies of population carboxy-hemoglobin levels are evaluated and compared with ambient air data.,

No significant correlation was found between median population COHb levels and reductions in CO concentrations required to meet ambient air standards when calculations used to estimate reductions were based on the second highest 8 hour average. However, calculated reductions based on annual average concentrations and a trend analysis technique correlated significantly with COHb levels in five cities from which both CAMP and COHb data were available.

Studies to determine the nature of the relationship between ambient air CO concentrations and population COHb levels are needed. The differences between the Occupational Safety and Health Act Regulations and the National Ambient Air Standards for carbon monoxide should be scrutinized to determine if a redefinition of the standards or their applicability is warranted. A reevaluation of the controls necessary to make reductions in population COHb burden may be necessary.     

Characterization of Particulates from Power Plants

The emphasis on participate control from industrial processes has been shifted recently towards fine particulates, having diameters less than 3 microns. There exists an urgent need for more scientific information of fine particle characterization.^1,2 Coal and oil fired power plants are among the largest anthropogenic point sources of particulate matter.³ Limited knowledge is available on particle size distribution and trace metal composition in power plant emissions.^4-7 The morphological properties of particle emissions have been largely neglected. In this report we present some information on particle characteristics for an oil-fired and coal-fired power plant.     

Heavy Duty Diesel Particulate Emission Factors

For the past several years, EPA has been measuring particulate emissions from a variety of heavy-duty diesel engines through contracts with Southwest Research Institute. Particulate emissions samples have been collected using an exhaust splitter to divert a fraction of the engine exhaust into a standard dilution tunnel. A small fraction of the diluted exhaust from the tunnel is pulled through a filter from which particulate mass and, in some cases, organic content of the particulate is determined. This paper discusses the sampling system and gives particulate emission factors that have been computed from truck and bus fuel consumption data as well as average truck and bus speed data from New York and Los Angeles (freeway and nonfreeway usage). Average particulate emission test results (steady state tests) for 2-stroke engines were 4.74 g/kg fuel and for 4-stroke engines were 2.64 g/kg fuel. Using average particulate emissions results, a particulate emission factor range of 0.8 to 1.3 g/km was computed. Nationwide diesel particulate emissions were calculated to be 88,000 metric tons per year.