Application of comprehensive two-dimensional gas chromatography with mass spectrometric detection for the analysis of selected drug residues in wastewater and surface water

Pharmaceutical residues have become tightly controlled environmental contaminants in recent years, due to their increasing concentration in environmental components. This is mainly caused by their high level of production and everyday consumption. Therefore there is a need to apply new and sufficiently sensitive analytical methods, which can detect the presence of these contaminants even in very low concentrations. This study is focused on the application of a reliable analytical method for the analysis of 10 selected drug residues, mainly from the group of non-steroidal anti-inflammatory drugs (salicylic acid, acetylsalicylic acid, clofibric acid, ibuprofen, acetaminophen, caffeine, naproxen, mefenamic acid, ketoprofen, and dicofenac), in wastewaters and surface waters. This analytical method is based on solid phase extraction, derivatization by N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) and finally analysis by comprehensive two-dimensional gas chromatography with Time-of-Flight mass spectrometric detection (GC×GC- TOF MS). Detection limits ranged from 0.18 to 5 ng/L depending on the compound and selected matrix. The method was successfully applied for detection of the presence of selected pharmaceuticals in the Svratka River and in wastewater from the wastewater treatment plant in Brno-Modrice, Czech Republic. The concentration of pharmaceuticals varied from one to several hundreds of ng/L in surface water and from one to several tens of μg/L in wastewater.     

Using lysosomal membrane stability of haemocytes in Ruditapes philippinarum as a biomarker of cellular stress to assess contamination by caffeine, ibuprofen, carbamazepine and novobiocin

Although pharmaceuticals have been detected in the environment only in the range from ng/L to g/L, it has been demonstrated that they can adversely affect the health status of aquatic organisms. Lysosomal membrane stability (LMS) has previously been applied as an indicator of cellular well-being to determine health status in bivalve mussels. The objective of this study is to evaluate LMS in Ruditapes philippinarum haemolymph using the neutral red retention assay (NRRA). Clams were exposed in laboratory conditions to caffeine (0.1, 5, 15, 50 μg/L), ibuprofen (0.1, 5, 10, 50 μg/L), carbamazepine and novobiocin (both at 0.1, 1, 10, 50 μg/L) for 35 days. Results show a dose-dependent effect of the pharmaceuticals. The neutral red retention time measured at the end of the bioassay was significantly reduced by 50% after exposure to environmental concentrations (p < 0.05) (caffeine = 15 μg/L; ibuprofen = 10 μg/L; carbamazepine = 1 μg/L and novobiocin = 1 μg/L), compared to controls. Clams exposed to these pharmaceuticals were considered to present a diminished health status (retention time < 45 min), significantly worse than controls (96 min) (p < 0.05). The predicted no environmental effect concentration (PNEC) results showed that these pharmaceuticals are very toxic at the environmental concentrations tested. Measurement of the alteration of LMS has been found to be a sensitive technique that enables evaluation of the health status of clams after exposure to pharmaceuticals under laboratory conditions, thus representing a robust Tier-1 screening biomarker.     

Warm forming die design,part I: Experimental validation of a novel thermal finite element modeling code

Finite element analysis (FEA) has become an invaluable tool in the design of sheet metal stamping dies and processes. FEA has gained widespread acceptance as the best method of optimizing dies for conventional stamping processes. More recently, FEA has been shown to be an effective method of designing tooling for sheet forming processes. In this work, an FEA based approach is applied to the warm stamping (warm forming) process. This work introduces a new thermal finite element analysis software called PASSAGE®/Forming (PASSAGE) that enables the up-front design of the thermal management of warm forming dies. This thermal finite element analysis software is designed to specifically handle the forming and optimization scenarios related to the heating of a stamping die while minimizing user interface time. In this work, PASSAGE has been applied to a simple block of steel embedded with cartridge heaters to validate the prediction capability of this software under two different heating conditions. The results show that PASSAGE is capable of predicting the actual steady-state temperature distribution within the block with an acceptable level of accuracy while yielding notable information to the user with respect to specifying power requirements. A finite element software package like PASSAGE is a valuable tool that will aid greatly in the implementation of warm forming as a manufacturing process beyond the scope of the laboratory and into production.     

Presence of Torque Teno Virus (TTV) in Tap Water in Public Schools from Southern Brazil

Torque teno virus (TTV) was surveyed in tap water collected in schools from three municipalities located in the south of Brazil. TTV genomes were found in 11.7 % (4/34) of the samples. TTV DNA was detected in 10.5 % (2/19) of the samples collected at the city of Caxias do Sul and in 25 % (2/8) of the samples from Pelotas. Those cities have a low rate of sewage treatment. All samples from Santa Cruz do Sul, which has nearly 92 % of its sewage treated, were negative. These results suggest that the amount of sewage treated may have an effect on the detection rates of TTV DNA in drinking water in a given urban area, showing a mild negative correlation (r = ?0.76), when comparing the percentage of sewage treatment to the detection of TTV genomes. The detection rate of TTV was also compared with Escherichia coli, showing a strong correlation (r = 0.97), indicating that TTV may be a suitable marker of fecal contamination.     

Influence of overlap between the laser beam tracks on surface quality in laser polishing of AISI H13 tool steel

Polishing by laser beam radiation is a novel manufacturing process to modify the initial surface topography in order to achieve a desired level of surface finish. The performance of laser polishing (LP) is determined by an optimum combination of several key process parameters. In this regard, the overlap between two successive laser beam tracks is one of the important LP process parameters, which has a significant effect over the final surface quality. In the current study, influence of overlap between the laser beam tracks on surface quality was experimentally investigated during the laser polishing of AISI H13 tool steel. Surface areas were polished by using four different overlap percentages (e.g. 80%, 90%, 95%, and 97.5%) while applying the same energy density. The improvement of surface quality was estimated through the analysis of line profiling surface roughness R_a, areal topography surface roughness S_a, and material ratio function. Also, individual components of the surface quality, e.g. waviness and roughness, and their evolution during LP were statistically analyzed using the power spectral density and the transfer functions. Finally, as an example of the best achieved LP result, flat surface area was polished using optimum set of the process parameters improving surface quality by 86.7% through the reduction of an areal topography surface roughness S_a from 1.35 μm to 0.18 μm.     

Prompting safety-belt use in the context of a belt-use law: the flash-for life revisited

PROBLEM: Safety-belt use reduces motor vehicle crash-related morbidity and mortality, yet an estimated 18% of drivers do not consistently buckle up (NHTSA, 2005). In 1985, Geller and colleagues developed an interpersonal Flash-for-Life prompt that increased belt use among 22% of 1,087 unbuckled drivers (Geller, Bruff, & Nimmer, 1985). METHOD: The Flash-for-Life intervention was re-introduced at a large university with high safety-belt use (i.e., 80%). College students stood at parking-lot entrance/exits and "flashed" signs with the message, "Please Buckle Up, I Care" to unbuckled drivers. RESULTS: Of 427 unbuckled drivers observed, 30% of these complied with the prompt. Male drivers were significantly more likely to comply with prompts delivered by females. DISCUSSION: Compliance was higher than in the 1985 study, indicating a high baseline rate of safety-belt use does not negate potential beneficial influence of a prompting intervention. This intervention is particularly effective with college-aged males, a sub-group of the driving population least likely to buckle-up. IMPACT ON INDUSTRY: A simple behavioral prompt could be used at most industrial complexes to increase safety-belt use among vehicle occupants who are not buckled-up.     

A new THOR shoulder design: a comparison with volunteers, the Hybrid III, and THOR NT

OBJECTIVE: Since the shoulders are rarely seriously injured in frontal or oblique collisions, they have been given low priority in the development of frontal impact crash test dummies. The shoulder complex geometry and its kinematics are of vital importance for the overall dummy kinematics. The shoulder complex also influences the risk of the safety belt slipping off the shoulder in oblique forward collisions. The first aim of this study was to develop a new 50th percentile male THOR shoulder design, while the second was to compare the new shoulder, mounted on a THOR NT dummy, with volunteer, THOR NT, and Hybrid III range of motion and stiffness data. The third aim was to test the repeatability of the new shoulder during dynamic testing and to see how the design behaves with respect to belt slippage in a 45 degrees far-side collision. METHODS: The new 50th percentile THOR shoulder design was developed with the aid of a shell model of the seated University of Michigan Transportation Research Institute (UMTRI) 50th percentile male with coordinates for joints and bony landmarks (Schneider et al., 1983). The new shoulder design has human-like bony landmarks for the acromion and coracoid processes. The clavicle curvature and length are also made similar to that of a male human, as is the range of motion in the anterior-posterior, superior-inferior, and medial-lateral directions. The new shoulder design was manufactured and tested under the same conditions that T?rnvall et al. (2005b) used to compare the shoulder range of motion for the volunteers, Hybrid III, and THOR Alpha. The new design was also tested in two dynamic test configurations: the first was a 0 degrees full-frontal test and the second was a 45 degrees far-side test. The dummy tests were conducted with an R-16 seat with a three-point belt, the Delta V was 27.0+/-0.5 km/h and the maximum peak acceleration was approximately 14.6+/-0.5 g for each test. RESULTS: A new shoulder design with geometry close to that of humans was developed to be retrofitted to the THOR NT dummy. The results showed that the range of motion for the new shoulder complex during static loading was larger by at least a factor of three, for the maximum load (200 N/arm), than that of either the Hybrid III or the THOR NT; this means it was more similar to the volunteers' range of motion. It was observed that the THOR NT with the new shoulder did not slide out of the shoulder belt during a far-side collision. The performance of the new shoulder was reasonably repeatable and stable during both the static tests and the sled tests. CONCLUSION: A new shoulder for the THOR NT has been designed and developed, and data from static range of motion tests and sled tests indicate that the new shoulder complex has the potential to function in a more human-like manner on the THOR dummy.     

Impact on sward composition and stock performance of grazing Molinia-dominant grassland

A comparative experiment was conducted to test the extent to which grazing of rank Molinia caerulea-dominated grassland increases botanical diversity and improves animal performance. The study was carried out on an area of under-grazed Molinia-dominant pasture that had not been stocked for 20 years. Three treatments were compared from 2001 until 2008: (1) no grazing, (2) grazing by Welsh Mountain sheep and (3) grazing by Welsh Black heifers. Patterns of change in sward surface composition across the grazing season were consistent with greater consumption of Molinia by the cattle, but there was little evidence of management regime influencing changes in sward composition year-on-year. There was a significant effect of year on animal performance (P < 0.001). Although the growth rates of the heifers improved over the course of the first three years of the experiment, this performance was not sustained. In contrast, any weight changes for the sheep were positive. The results highlight the slow pace of change within upland swards, and the need to develop site-specific grazing guidelines.     

Evidence of rich microbial communities in the subsoil of a boreal acid sulphate soil conducive to greenhouse gas emissions

The largest areas of acid sulphate (AS) soils in Europe are located in Finland, where 67,000–130,000 ha of AS soils are in agricultural use. In addition to their acidifying effects on waters, AS soils might be a significant source of greenhouse gases. In this pilot research, carbon and nitrogen content and microbial activity were studied in an AS and a non-AS soil. Large carbon and nitrogen stocks (110 Mg C_org ha^?1 and 15 Mg N_tot ha^?1) as well as high substrate induced respiration (33 μg CO₂–C g^?1h^?1) were found in the C horizons of the AS soil but not in the non-AS soil. High microbial activity in these horizons of the AS soil was further confirmed by the measurement of dehydrogenase activity, basal respiration, the numbers of culturable bacterial cells, and the ratio of culturable to total numbers of cells. Still, the denitrifying enzyme activity was very low in the anaerobic horizons of the AS soil, indicating the prevalence of microbes other than denitrifiers. We suspect that the microbial community originated with the genesis of AS soil and has been supported by the large stocks of accumulated carbon and mineral nitrogen in the C horizons. If these permanently water-saturated subsoils are exposed to oxygen and their microbial activity consequently increases, large carbon and nitrogen stocks are likely to be mobilised, resulting in increased emission of greenhouse gases. Additional studies of boreal AS soils are needed to assess their potential contribution to increases in greenhouse gas fluxes at the local, regional, and global scales.     

Assays with Daphnia magna and Danio rerio as alert systems in aquatic toxicology

For the evaluation and monitoring of the water quality, a series of methodologies, which have as basis an ample variety of bioindicators, may be applied. The aim of this research was to evaluate the use of ecotoxicity assays with Daphnia magna and Danio rerio as alert systems in water contaminated with toxic substances. Using two toxicity databases, the sensibility of those aquatic organisms to a wide variety of chemical products and elements and to some chemical categories was investigated. The relation between the reference dose for human oral chronic exposure (RfD) of all chemical products and the acute toxicity values for both bioindicators was also studied. Acute toxicity tests with D. magna respond to a larger variety of chemicals with a higher sensitivity than those with D. rerio. Although mammals, crustaceans and fish have different routes of exposure, target organs and toxic mechanisms, acute toxicity essays with fish and Daphnia may be used as an initial screening before mammal models are used.