Environmental risk assessment of human pharmaceuticals in Denmark after normal therapeutic use

An environmental risk assessment is presented for the 25 most used pharmaceuticals in the primary health sector in Denmark. Predicted environmental concentrations (PECs) for the aquatic environment were calculated using conservative assumptions and all PECs exceeded 1 ng/l. Measured concentrations were in general within a factor of 2-5 of PECs and ranged from approximately 0.5 ng/l to 3 micrograms/l for nine of the pharmaceuticals reported in literature. The calculation of predicted no-effect concentration (PNEC) based on aquatic ecotoxicity data was possible for six of the pharmaceuticals. PEC/PNEC ratio exceeded one for ibuprofen, acetylsalicylic acid, and paracetamol. For estrogens the PEC/PNEC ratio approached one when non-standard test was used. The ratio was below one for estrogens (standard test), diazepam and digoxin. For the terrestrial compartment, toxicity data were not available, and no assessment was carried out. Comparisons of predicted concentrations of furosemide, ibuprofen, oxytetracycline and ciprofloxacin in sludge based on either preliminary experimental sludge-water partition coefficients (Kd), octanol-water coefficients (Kow) or acid-base constants (pKa) revealed large variations.     

Duplicate sampling reproducibility of atmospheric residues of herbicides for paired pan and high-volume air samplers

The reproducibility of collection of atmospheric residues of the herbicides 2,4-D and triallate as bulk (wet plus dry) deposition samples by paired pan samplers and as particulate (filter) and vapour (PUF/XAD-2 resin cartridge) samples by paired high-volume air samplers was determined. Variability of herbicide concentrations in paired bulk deposition samples was within 25% for 65 and 80% of the samples for 2,4-D and triallate, respectively, with approximately 90% of the paired samples being within a factor of 2 for both herbicides. The vapour samples of 2,4-D and triallate showed similar reproducibilities. The highest reproducibility was observed for the filter samples with 92% of the paired data sets for 2,4-D being within 25% variability. No triallate was detected in the filter samples.     

The sensitivity of PM2.5 source-receptor relationships to atmospheric chemistry and transport in a three-dimensional air quality model

Air quality model simulations constitute an effective approach to developing source-receptor relationships (so-called transfer coefficients in the risk analysis framework) because a significant fraction of particulate matter (particularly PM2.5) is secondary (i.e., formed in the atmosphere) and, therefore, depends on the atmospheric chemistry of the airshed. In this study, we have used a comprehensive three-dimensional air quality model for PM2.5 (SAQM-AERO) to compare three approaches to generating episodic transfer coefficients for several source regions in the Los Angeles Basin. First, transfer coefficients were developed by conducting PM2.5 SAQM-AERO simulations with reduced emissions of one of four precursors (i.e., primary PM, sulfur dioxide (SO2), oxides of nitrogen (NOx), and volatile organic compounds) from each source region. Next, we calculated transfer coefficients using two other methods: (1) a simplified chemistry for PM2.5 formation, and (2) simplifying assumptions on transport using information limited to basin-wide emission reductions. Transfer coefficients obtained with the simplified chemistry were similar to those obtained with the comprehensive model for VOC emission changes but differed for NOx and SOz emission changes. The differences were due to the parameterization of the rates of secondary PM formation in the simplified chemistry. In 90% of the cases, transfer coefficients estimated using only basin-wide information were within a factor of two of those obtained with the explicit source-receptor simulations conducted with the comprehensive model. The best agreement was obtained for VOC emission changes; poor agreement was obtained for primary PM2.5.     

Results of an "emergency quality control study" as confirmation of a PCDD/PCDF-contamination of milk and butter samples

Elevated PCDD/F levels in four butter samples and one milk sample had to be confirmed under considerable time pressure. These samples should demonstrate a raising dioxin contamination in different regions of Germany caused by the use of Brazilian citrus pulp as feedstuff. Above all, the increase of 2,3,7,8-TCDD and 1,2,3,7,8-PeCDD had to be confirmed. Thus, an "emergency quality control study" was performed including five laboratories from the official food control in Germany. The results had to be reported about two to three weeks after the first announcement of the samples (including time for shipment). The five laboratories applied different extraction and clean-up methods, used different GC-columns and GC/MS-equipment and different standard solutions. The results are in a good agreement. Slightly different results for most individual congeners were of minor importance. A difference was observed only in the 2,3,7,8-TCDF content of one laboratory which was not relevant for the evaluation of the increase of the dioxin contamination in milk and dairy products. The laboratory's individual methods proved to give correct results even under a very tight schedule.     

Decrease of PCDD/F levels in human blood from Germany over the past ten years (1989-1998)

744 whole blood samples of normal subjects from Germany collected in 1989-1998 have been analyzed for polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) by capillary gas chromatography/high resolution mass spectrometry. Over the examined time period a continuous decrease of the PCDD/F concentrations in human blood was observed. The mean levels found were 43.7 pg I-TEq/g (lipid basis) in 1989 and 20.7 pg I-TEq/g (lipid basis) in 1996/98 [median: 42.2 and 19.4]. The reduction to about the half was found for most congeners. Each one-year subset of the collective and the entire collective shows a positive correlation of the PCDD/F blood levels with age for most of the congeners, the sum values and the calculated toxicity equivalents. For statistical evaluation a multiplicative model was used: Concentration = A x Age(B). The correlation is mostly pronounced for lower chlorinated PCDD and for 2,3,4,7,8-PentaCDF. The PCDD/F concentrations in human blood in relation to the year of examination and the age of the subjects can be described by a linear model: I-TEq [pg/g (lipid basis)] = 6176 - 3.097 x Year + 0.6482 x Age or by a multiplicative model: I-TEq [pg/g(lipid basis)] = 10(89.08-0.04415 x Year + 0.008468 x Age).     

Levels of toxaphene congeners in fish from Danish waters

The levels of toxaphene congeners, in addition to PCB congeners and organochlorine pesticides, were determined in various fish samples from different Danish waters. While PCB-153 and p,p'-DDE show different levels depending on the fishing area, with highest levels in fish from the Western Baltic Sea, toxaphene was detected in all the samples investigated at a more constant level. The distribution of the three toxaphene congeners Parlar #26, #50 and #62 depends on the fishing area, with the Western Baltic Sea being different from the other waters by having almost equal levels of toxaphene congeners #26 and #50.     

Effect of methyl tertiary butyl ether concentrations on exhaust emissions from gasoline used in the metropolitan area of Mexico City

In this work, the primary objective was to assess the impact of oxygenated fuel on the exhaust emissions from an important fraction of vehicles in the Metropolitan Area of Mexico City (MAMC). The results aim to provide information on the actual effect of MTBE on a fleet that represents more than 60% of the in-use vehicles in the MAMC. Ten vehicles were tested with a low-octane base gasoline, and 10 more with a regular-grade unleaded base gasoline. Three MTBE concentrations, 5, 10, and 15 vol %, were tested following the U.S. Federal Test Procedure (FTP). CO, total HC, and NOx from the exhaust gases were quantitatively evaluated and also characterized for FTP speciated organic emissions. From this data, the O3-forming potential of the fuels was calculated. Results show that for the fleet using low-octane gasoline, the addition of 10% MTBE substantially reduced CO emissions, but total HC concentration in the exhaust showed a modest decrease. For the regular gasoline, the 10% MTBE blend seemed to be the best choice, but there was not a significant decrease in emissions. The specific reactivity of each fuel, expressed in grams of O3 per gram of nonmethane organic gases, increased with MTBE concentration in both cases. This result is important to consider, especially for a region like Mexico City, which has high atmospheric O3 concentrations.     

Impact of long-term pesticide applications on some soil biological parameters

The soil oxidative and anaerobic processes, as well as, the microbial biomass were followed during three years in a cotton farm (Tatuí) where the recommended pesticides have been used for several years, and in an experimental field (S?o Paulo) treated first time with the same pesticides. The oxidative process was monitored by the dehydrogenase (DHA)-activity using triphenyltetrazolium chloride (TTC) as substrate. The anaerobic process was followed by the iron-oxide reduction, and the microbial biomass was estimated by the substrate (glucose)-indiced respiration. Increases in DHA-activity and in the microbial biomass occurred only in the farm soil, with concomitant decreases in iron-reduction. In the experimental field soil, the increases in DHA-activity were followed only by decreases in iron-reduction. Soil characteristics were the determining factor for different biological parameters after pesticide inputs. All the pesticides produced at least one clear but transient effect.     

Effects of metabolites of benzo(a)pyrene on unschedule DNA synthesis in BALB/3T3 cell line

In order to explore the damage from metabolites of benzo(a)pyrene on DNA of mammalian cells, the effects of four metabolites of benzo(a)pyrene (anti-BPDE, syn-BPDE, 3-OH-BP and 9-OH-BP) on synthesis of DNA and unschedule DNA synthesis (UDS) in BALB/3T3 cells were assayed, by methods of single-labeling and double-labeling. The results showed that all of the four agents were able to increase the synthesis of DNA, but only three of them (apart from syn-BPDE) induced UDS in BALB/3T3 cells. The above indicates that the metabolites of benzo(a)pyrene are able to damage DNA in BALB/3T3 cells, and that this effect may be relative to the sterical structure of metabolites of benzo(a)pyrene.     

Congener-specific analysis of toxaphene in eggs of seabirds from Germany by HRGC-NCI-MS using a carborane-siloxane copolymer phase (HT-8)

A method for the congener-specific analysis of toxaphene in eggs of seabirds from a monitoring program from the northern part of Germany was carried out. The method was optimized in most steps of the procedure: injection temperature, HRGC with an HT-8 column, ion source temperature and the MS detection mode NCI/SIM measuring the isotope clusters of [M] , [M-Cl]-, [M-HCl]- and [M-2Cl]-. The suitability of 1,4-exo, 7,8,9,10,10-heptachloro-5-methoxytricyclo [5,2,1,0(2,6)]dec-3,8-diene as internal standard was demonstrated. 14 toxaphenes with Parlar numbers and more than 60 unknown toxaphenes could be identified. Spatial and temporal trends of toxaphene contamination are presented by using the Parlar 22 components standard for quantification.