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.     

A Multipurpose Flare Stack for Control of Chemical Process Wastes

Abstract

To test the effectiveness of California’s vehicle inspection/ maintenance (I/M) program, exclusive of vehicle-owner intervention, a fleet of more than 1,100 vehicles that previously had failed California’s Smog Check test were sent to randomly selected Smog Check stations in the Los Angeles area for covert inspections and repairs. The two-speed idle test was used for repairs. For those vehicles that were repaired at the first inspection, their FTP emission reductions were 25%, 14%, and 11% for hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NO_x), respectively, although emissions testing for NO_x was not performed at the Smog Check stations. Idle HC and CO emissions increased for 35% and 43% of the vehicles, respectively, after repairs. This data set shows that most vehicles that fail the Smog Check inspection are only marginal emitters, with 61% and 44% of the total potential for HC and CO emission reductions, respectively, coming from only 10% of the vehicles that currently fail the inspection. When the vehicles were rank-ordered by idle emissions from dirtiest to cleanest, emission reduction costs for the highest-emitting 10% of the fleet averaged $l,100/ton and $250/ton for HC and CO, respectively, attributing all the costs to each pollutant exclusively. For the remaining vehicles, costs increased dramatically.     

Measurement of Automobile Exhaust GAS Hydrocarbons

While snowflakes fell and Christmas carols heralded the imminent holiday, over 3000 delegates to the Third National Conference on Air Pollution were told to “Control Now for Clean Air.”

They were told this in many ways by many people—by the Vice President of the United States; by the Secretary of the Department of Health, Education, and Welfare who summoned the Conference; and by senators, congressmen, governors, and mayors.

Then eight panel sessions convened to discuss and to determine how to control now for clean air. Speakers from every section of American life addressed themselves to this subject; when they were finished, the eight session chairmen summarized what had been said, what had been, learned. These summaries appear on the following pages.     

Empirical models based on the universal soil loss equation fail to predict sediment discharges from Chesapeake Bay catchments

The Universal Soil Loss Equation (USLE) and its derivatives are widely used for identifying watersheds with a high potential for degrading stream water quality. We compared sediment yields estimated from regional application of the USLE, the automated revised RUSLE2, and five sediment delivery ratio algorithms to measured annual average sediment delivery in 78 catchments of the Chesapeake Bay watershed. We did the same comparisons for another 23 catchments monitored by the USGS. Predictions exceeded observed sediment yields by more than 100% and were highly correlated with USLE erosion predictions (Pearson r range, 0.73-0.92; p < 0.001). RUSLE2-erosion estimates were highly correlated with USLE estimates (r = 0.87; p < 001), so the method of implementing the USLE model did not change the results. In ranked comparisons between observed and predicted sediment yields, the models failed to identify catchments with higher yields (r range, -0.28-0.00; p > 0.14). In a multiple regression analysis, soil erodibility, log (stream flow), basin shape (topographic relief ratio), the square-root transformed proportion of forest, and occurrence in the Appalachian Plateau province explained 55% of the observed variance in measured suspended sediment loads, but the model performed poorly (r(2) = 0.06) at predicting loads in the 23 USGS watersheds not used in fitting the model. The use of USLE or multiple regression models to predict sediment yields is not advisable despite their present widespread application. Integrated watershed models based on the USLE may also be unsuitable for making management decisions.     

Acrylamide monomer leaching from polyacrylamide-treated irrigation furrows

Water-soluble anionic polyacrylamide (WSPAM), which is used to reduce erosion in furrow irrigated fields and other agriculture applications, contains less than 0.05% acrylamide monomer (AMD). Acrylamide monomer, a potent neurotoxicant and suspected carcinogen, is readily dissolved and transported in flowing water. The study quantified AMD leaching losses from a WSPAM-treated corn (Zea mays L.) field using continuous extraction-walled percolation samplers buried at 1.2 m depth. The samplers were placed 30 and 150 m from the inflow source along a 180-m-long corn field. The field was furrow irrigated using WSPAM at the rate of 10 mg L(-1) during furrow advance. Percolation water and furrow inflows were monitored for AMD during and after three furrow irrigations. The samples were analyzed for AMD using a gas chromatograph equipped with an electron-capture detector. Furrow inflows contained an average AMD concentration of 5.5 microg L(-1). The AMD in percolation water samples never exceeded the minimum detection limit and the de facto potable water standard of 0.5 microg L(-1). The risk that ground water beneath these WSPAM-treated furrow irrigated soils will be contaminated with AMD appears minimal.     

Physical and chemical changes during composting of wood chip-bedded and straw-bedded beef cattle feedlot manure

In the 1990s, restrictions on incineration encouraged the forest industry in western Canada to develop new uses for their wood residuals by product. One such use was as a replacement for cereal straw bedding in southern Alberta's beef cattle (Bos taurus) feedlot industry. However, use of carbon (C)-rich bedding, such as wood chips, had implications for subsequent composting of the feedlot manure, a practice that was being increasingly adopted. In a 3-yr study, we compared composting of wood chip-bedded manure (WBM) and barley (Hordeum vulgare L.) straw-bedded manure (SBM). There were no significant differences in temperature regimes of SBM and WBM, indicating similar rates of successful composting. Of 17 physical and chemical parameters, five showed significant (P < 0.10) differences due to bedding at the outset of composting (Day 0), and 11 showed significant differences at final sampling (Day 124). During composting (10 sampling times), seven parameters showed significant bedding effects, 16 showed significant time effects, and four showed a Bedding x Time interaction. Significantly lower (P < 0.10) losses of nitrogen (N) occurred with WBM (19%) compared with SBM (34%), which has positive implications for air quality and use as a soil amendment. Other advantages of WBM compost included significantly higher total C (333 vs. 210 kg Mg(-1) for SBM) and inorganic N (1.3 vs. 1.0 kg Mg(-1) for SBM) and significantly lower total phosphorus (4.5 vs. 5.3 kg Mg(-1) for SBM). Our results showed that wood chip bedding should not be a problem for subsequent composting of the manure after pen cleaning. In combination with other benefits, our findings should encourage the adoption of wood chips over straw as a bedding choice for southern Alberta feedlots.     

In situ transmissiometer measurements for real-time monitoring of dust discharge during orchard nut harvesting

Rapid assessments of operating conditions and field preparation on dust discharge from nut harvesters are needed to guide improved equipment design and grower practices for dust reduction. An industrial opacity sensor, typically used for industrial stack monitoring, was adapted for use on a nut harvester to measure relative dust intensity during nut pick-up operations in almond orchards. Due to the high volume of discharge air and the presence of large debris such as leaves, additional components were coupled with the sensor to enable subsampling of the air. Pre-harvest windrow preparation conditions were evaluated. Results indicated that relative dust intensity decreased by 32% during harvest activities after windrow preparation with proper nut sweeper adjustment. Conventional harvesting results indicated that under typical operating conditions, reducing the separation fan speed could reduce relative dust intensity by 54%. Ground speed also had a strong effect; reducing speed from 4.8 to 2.4 km h(-1) reduced opacity of discharged air by 50%. The measurement system was also mounted on a separate vehicle and used as a tool for comparing modifications in harvest machine designs where direct measurement of discharge may not be feasible due to mechanical constraints. A comparison between a conventional harvester and one modification in the harvester design found that the machine modification decreased relative dust intensity by 73%. The measurement tools described in this work can be used to provide rapid feedback on harvester operating conditions, orchard cultural practices, and machine design modifications.     

Life cycle assessment of waste paper management: The importance of technology data and system boundaries in assessing recycling and incineration

The significance of technical data, as well as the significance of system boundary choices, when modelling the environmental impact from recycling and incineration of waste paper has been studied by a life cycle assessment focusing on global warming potentials. The consequence of choosing a specific set of data for the reprocessing technology, the virgin paper manufacturing technology and the incineration technology, as well as the importance of the recycling rate was studied. Furthermore, the system was expanded to include forestry and to include fossil fuel energy substitution from saved biomass, in order to study the importance of the system boundary choices. For recycling, the choice of virgin paper manufacturing data is most important, but the results show that also the impacts from the reprocessing technologies fluctuate greatly. For the overall results the choice of the technology data is of importance when comparing recycling including virgin paper substitution with incineration including energy substitution. Combining an environmentally high or low performing recycling technology with an environmentally high or low performing incineration technology can give quite different results. The modelling showed that recycling of paper, from a life cycle point of view, is environmentally equal or better than incineration with energy recovery only when the recycling technology is at a high environmental performance level. However, the modelling also showed that expanding the system to include substitution of fossil fuel energy by production of energy from the saved biomass associated with recycling will give a completely different result. In this case recycling is always more beneficial than incineration, thus increased recycling is desirable. Expanding the system to include forestry was shown to have a minor effect on the results. As assessments are often performed with a set choice of data and a set recycling rate, it is questionable how useful the results from this kind of LCA are for a policy maker. The high significance of the system boundary choices stresses the importance of scientific discussion on how to best address system analysis of recycling, for paper and other recyclable materials.     

Projecting Cumulative Benefits of Multiple River Restoration Projects: An Example from the Sacramento-San Joaquin River System in California

Despite increasingly large investments, the potential ecological effects of river restoration programs are still small compared to the degree of human alterations to physical and ecological function. Thus, it is rarely possible to “restore” pre-disturbance conditions; rather restoration programs (even large, well-funded ones) will nearly always involve multiple small projects, each of which can make some modest change to selected ecosystem processes and habitats. At present, such projects are typically selected based on their attributes as individual projects (e.g., consistency with programmatic goals of the funders, scientific soundness, and acceptance by local communities), and ease of implementation. Projects are rarely prioritized (at least explicitly) based on how they will cumulatively affect ecosystem function over coming decades. Such projections require an understanding of the form of the restoration response curve, or at least that we assume some plausible relations and estimate cumulative effects based thereon. Drawing on our experience with the CALFED Bay-Delta Ecosystem Restoration Program in California, we consider potential cumulative system-wide benefits of a restoration activity extensively implemented in the region: isolating/filling abandoned floodplain gravel pits captured by rivers to reduce predation of outmigrating juvenile salmon by exotic warmwater species inhabiting the pits. We present a simple spreadsheet model to show how different assumptions about gravel pit bathymetry and predator behavior would affect the cumulative benefits of multiple pit-filling and isolation projects, and how these insights could help managers prioritize which pits to fill.     

Relationships between street characteristics and perceived attractiveness for walking reported by elderly people

Walking is important for the health of elderly people. Previous studies have found a relationship between neighbourhood characteristics, physical activity and related health aspects. The multivariate linear regression model presented here describes the relationships between the perceived attractiveness of streets for walking along and (physical) street characteristics. Two hundred and eighty-eight independently living elderly people (between 55 and 80 years old) participated in the study. Street characteristics were assessed along homogeneous street subsections defined as ‘links’. Positively related to perceived attractiveness of links were the following street characteristics: slopes and/or stairs, zebra crossings, trees along the route, front gardens, bus and tram stops, shops, business buildings, catering establishments, passing through parks or the city centre, and traffic volume. Litter on the street, high-rise buildings, and neighbourhood density of dwellings were negatively related to perceived link attractiveness. Overall, the results suggest that three main aspects affect perceived attractiveness of streets for walking, namely tidiness of the street, its scenic value and the presence of activity or other people along the street. The results are discussed within the context of these three aspects.