Modeling the impact of direct phototransformation on predicted environmental concentrations (PECs) of propranolol hydrochloride in UK and US rivers

There is currently uncertainty on the persistence of active pharmaceutical ingredients (APIs) and on their depletion mechanisms in natural surface waters such as rivers, and hence predictions of their fate are often poor. In this study, a beta-adrenergic receptor, propranolol hydrochloride, was selected as a model API to explore the relative significance of direct phototransformation as a potential removal process of hydrophilic APIs in rivers. Phototransformation kinetics of propranolol was measured under simulated solar irradiation in the laboratory, which were then converted to the kinetics applicable in UK and US rivers. The effects of light intensity, light penetration, river size and flow were examined. The extrapolated phototransformation half-lives were applied in the river catchment models of GREAT-ER and PhATE. Results demonstrated that direct phototransformation significantly reduced the predicted environmental concentrations of propranolol in the water phase. Predicted reductions of mean concentrations in the River Aire (UK) were 27% in summer and 3% in winter; and for the US rivers simulated, reductions were 28-68% in summer and 11-41% in winter. The highest reductions were predicted for long rivers with low turbidity and low flow conditions.     

The historical record of PCB and PCDD/F deposition at Greifensee, a lake of the Swiss plateau, between 1848 and 1999

Dated sediment cores provide an excellent way to investigate the historical input of persistent organic pollutants into the environment and to identify possible sources of pollution. The vertical distribution of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/F) and polychlorinated biphenyls (PCB) was investigated in a sediment core from Greifensee to elucidate the historical trends of PCDD/F and PCB inputs between 1848 and 1999. Concentrations of PCB and PCDD/F increased by more than one order of magnitude between 1930 and 1960. PCB and PCDD/F concentrations were 5700 ng/kg dry weight (dw) and 160 ng/kg dw, respectively, in sediments originating from the late 1930s and reached a maximum of 130,000 ng/kg dw and 2400 ng/kg dw, respectively, in the early 1960s. From 1960 on, concentrations decreased to the 1930s level by the mid 1980s. A remarkable shift in the PCDD/F pattern was observed after the early 1940s. Before 1940, the PCDD/F pattern was PCDF dominated (ratio of PCDD to PCDF=0.41+/-0.11), while the PCDD started to be the major species after the early 1940s (ratio of PCDD to PCDF=1.46+/-0.38). The temporal trends of PCB and PCDD/F correlate surprisingly well with each other. This might be due to the coincidence of two factors. The introduction of PCB on the market in the 1930s resulted in emissions due to the widespread use of these industrial chemicals. In the same time period, waste incineration became an increasingly popular way to get rid of garbage, boosting the PCDD/F emissions significantly. The rapid decline of PCDD/F and PCB concentrations in the sediment starting in the early 1960s reflects the result of better emission control techniques in thermal processes and the improvement of waste water treatment in the catchment of Greifensee.     

Application of microbial hot spots enhances pesticide degradation in soils

Through transfer of an active, isoproturon degrading microbial community, pesticide mineralization could be successfully enhanced in various soils under laboratory and outdoor conditions. The microbes, extracted from a soil having high native ability to mineralize this chemical, were established on expanded clay particles and distributed to various soils in the form of microbial "hot spots". Both, diffusion controlled isoproturon mass flow towards these "hot spots" (6microg d(-1)) as well as microbial ability to mineralize the herbicide (approximately 5microg d(-1)) were identified as the main processes enabling a multiple augmentation of the native isoproturon mineralization even in soils with heavy metal contamination. Soil pH-value appears to exert an important effect on the sustainability of this process.     

Isolation and characterization of 1,2,4-trichlorobenzene mineralizing Bordetella sp. and its bioremediation potential in soil

A soil which has been polluted with chlorinated benzenes for more than 25 years was used for isolation of adapted microorganisms able to mineralize 1,2,4-trichlorobenzene (1,2,4-TCB). A microbial community was enriched from this soil and acclimated in liquid culture under aerobic conditions using 1,2,4-TCB as a sole available carbon source. From this community, two strains were isolated and identified by comparative sequence analysis of their 16S-rRNA coding genes as members of the genus Bordetella with Bordetella sp. QJ2-5 as the highest homological strain and with Bordetella petrii as the closest related described species. The 16S-rDNA of the two isolated strains showed a similarity of 100%. These strains were able to mineralize 1,2,4-TCB within two weeks to approximately 50% in liquid culture experiments. One of these strains was reinoculated to an agricultural soil with low native 1,2,4-TCB degradation capacity to investigate its bioremediation potential. The reinoculated strain kept its biodegradation capability: (14)C-labeled 1,2,4-TCB applied to this inoculated soil was mineralized to about 40% within one month of incubation. This indicates a possible application of the isolated Bordetella sp. for bioremediation of 1,2,4-TCB contaminated sites.     

Desorption of PCDD/PCDF from municipal solid waste incinerator flyash under post-combustion plant conditions

The influence of temperature on the levels of PCDD and PCDF remaining in, and desorbed from, a municipal solid waste incinerator flyash was investigated by heating the ash to between 200 and 400 degrees C under a simulated flue gas for four days reaction time. Considerable desorption of PCDD/PCDF from the flyash was seen at 275 degrees C and above. Maximum desorption occurred at 350 degrees C, with the equivalent of nearly eight times the total PCDD/PCDF concentration of the original flyash being lost to the vapour phase per unit mass of initial flyash. The I-TEQ value of the desorbed PCDD/PCDF was considerable, being over fourteen times that of the original flyash at 325 degrees C. The results indicate that formation of PCDD/PCDF on flyash deposits in the post-combustion plant of incinerators can result in the release of significant amounts of PCDD/PCDF to the flue gas stream.     

Risk assessment of linear alkylbenzene sulphonates, LAS, in agricultural soil revisited: robust chronic toxicity tests for Folsomia candida (Collembola), Aporrectodea caliginosa (Oligochaeta) and Enchytraeus crypticus (Enchytraeidae)

To obtain robust data on the toxicity of LAS, tests with the collembolan Folsomia candida L., the oligochaetes Aporrectodea caliginosa Savigny (earthworm) and Enchytraeus crypticus Westheide and Graefe (enchytraeid) were performed in a sandy loam soil. Additionally limited tests with LAS spiked to sewage sludge, and subsequently mixed into soil, were performed. For the endpoint of interest, reproduction in soil, we found an EC10 of 205 mg LAS kg(-1) soil [8.6-401] [95% confidence limits] for F. candida and an EC10 of 46 mg LAS kg(-1) soil [13-80] for A. caliginosa after 28 days. E. crypticus was not affected by concentrations up to 120 mg LAS kg(-1) soil. When adding (low contaminated) non-spiked sludge to soil, high stimulation of reproduction was observed for E. crypticus and A. caliginosa but not for F. candida. We argue that this difference in stimulative response between the tested species is related to the difference in feeding behaviour. Sludge spiked with LAS did not significantly affect the reproduction of F. candida (fertility: number of juvenile offspring) and A. caliginosa (fecundity: number of cocoons) (dose equivalent to 181 g and 91 g LAS kg(-1) sludge, respectively). Significantly reduced reproduction was observed for E. crypticus (at 120 mg LAS kg(-1) soil+sludge corresponding to 72 g LAS kg(-1) sludge) compared to non-spiked sludge. The reproduction by E. crypticus was, however, comparable to the reproduction observed in the control soil without sludge. Compared to LAS directly spiked to soil, the reproductive output of organisms exposed to spiked sludge was either not significantly different (F. candida, E. crypticus) or significantly improved (A. caliginosa). More studies are needed in order to make firm conclusions on the potential effect of artificially contaminated sludge in soil systems.     

Evaluation of hydrophobicity in PAH-contaminated soils during phytoremediation

The impact of recalcitrant organic compounds on soil hydrophobicity was evaluated in contaminated soil from a manufactured gas plant site following 12 months of phytoremediation. Significant reduction in soil wetting and water retention was observed in contaminated soil compared to an uncontaminated control. Phytoremediation was effective at reducing total PAHs by 69% with corresponding changes in soil classification from extremely hydrophobic (initial sample) to moderately-strongly hydrophobic (planted) and hydrophilic-very hydrophilic (unplanted) after 12 months. The greatest reduction in soil hydrophobicity was observed in the unplanted, unfertilized treatments that had the lowest removal rate of PAHs. The presence of plants may contribute to hydrophobicity in contaminated soil.     

Combined effect of copper and prolonged summer drought on soil microarthropods in the field

Soil microarthropods experience a large range of natural stressors in their natural environment, e.g. variations in temperature and soil moisture, but also anthropogenic stressors such as soil pollutants. In the present study the combined effect of drought stress and copper pollution on microarthropods was investigated in a field study. We hypothesised that microarthropods in copper polluted soil would be more susceptible to drought than animals in control soil. Surprisingly, the abundance of microarthropods in autumn was positively affected by summer drought and copper pollution did not influence the effect of drought in a negative way. The stimulation was mainly seen as an increase of Acari, but also groups of Collembola were positively affected. We suggest that the positive effect of the enforced summer drought could be due to a rapid recovery, which further is accelerated by an increase of food resources (microbes) which have not been utilized during the drought.     

Biohydrogen production through fermentation using liquid swine manure as substrate

In this paper, continuous production of hydrogen through fermentation with liquid swine manure as substrate was researched using a semi-continuously fed fermenter (8 L in total volume and 4 L in working volume). The pH and temperature for the fermenter were controlled at 5.3 +/- 0.1 and 35 +/- 1 degrees C, respectively, throughout the experiment. Three hydraulic retention times (16, 20, and 24 h) were investigated for their impact on the efficiency and performance of the fermenter in terms of hydrogen yields. The results indicate that hydraulic retention time (HRT) has a strong influence on the fermenter performance. An increasing HRT would increase the variation in hydrogen concentration in the offgas. To produce hydrogen with a fairly consistent concentration, the HRT of the fermenter should not exceed 16 h, which, however, did not appear to be short enough to control methanogenesis because the offgas still contained about 5% methane. When methane content in the offgas exceeded 2%, an inverse linear relationship between hydrogen and methane was observed with a correlation coefficient of 0.9699. To increase hydrogen content in the offgas, methane production has to be limited to below 2%. Also, keeping oxygen content in the fermenter below 1.5% would increase the hydrogen concentration to over 15%. The product to substrate ratio was found to be around 50% for the fermenter system studied, evidenced by the observation that for every 6 liters of manure fermented, 3 liters of pure hydrogen were produced, which was significant and encouraging.     

Real-time measurement of outdoor tobacco smoke particles

The current lack of empirical data on outdoor tobacco smoke (OTS) levels impedes OTS exposure and risk assessments. We sought to measure peak and time-averaged OTS concentrations in common outdoor settings near smokers and to explore the determinants of time-varying OTS levels, including the effects of source proximity and wind. Using five types of real-time airborne particle monitoring devices, we obtained more than 8000 min worth of continuous monitoring data, during which there were measurable OTS levels. Measurement intervals ranged from 2 sec to 1 min for the different instruments. We monitored OTS levels during 15 on-site visits to 10 outdoor public places where active cigar and cigarette smokers were present, including parks, sidewalk cafés, and restaurant and pub patios. For three of the visits and during 4 additional days of monitoring outdoors and indoors at a private residence, we controlled smoking activity at precise distances from monitored positions. The overall average OTS respirable particle concentration for the surveys of public places during smoking was approximately 30 microg m(-3). OTS exhibited sharp spikes in particle mass concentration during smoking that sometimes exceeded 1000 microg m(-3) at distances within 0.5 m of the source. Some average concentrations over the duration of a cigarette and within 0.5 m exceeded 200 microg m(-3), with some average downwind levels exceeding 500 microg m(-3). OTS levels in a constant upwind direction from an active cigarette source were nearly zero. OTS levels also approached zero at distances greater than approximately 2 m from a single cigarette. During periods of active smoking, peak and average OTS levels near smokers rivaled indoor tobacco smoke concentrations. However, OTS levels dropped almost instantly after smoking activity ceased. Based on our results, it is possible for OTS to present a nuisance or hazard under certain conditions of wind and smoker proximity.