A fate constant data program

A program for compiling equilibrium and kinetic constants for predicting chemical transport and transformation in the environment is described. The fate constant data are obtained by searching the literature for reported measurements, by convening a panel of experts to postulate transformation pathways and products, by using computational techniques to estimate values, and by performing laboratory studies when measurements cannot be found or computed. Emphasis is placed throughout the program on quality control features to assure the reliability of the data.     

Levels and trends of industrial chemicals (PCBs, PFCs, PBDEs) in archived herring gull eggs from German coastal regions

Background

Polychlorinated biphenyls [PCBs], perfluorinated compounds, and polybrominated diphenyl ethers [PBDEs] were retrospectively analyzed in archived herring gull (Larus argentatus) eggs from the North and the Baltic Sea over the last 20 years. The aim was to assess temporal trends and effects of regulatory measures.

Results

PCBs (sum of 7 congeners) were highest in eggs from the North Sea island Trischen, i.e., 3,710 to 20,760 ng/g lipid weight [lw] compared to 2,530 to 11,650 ng/g lw on the North Sea island Mellum and 4,840 to 9,190 ng/g lw on the Baltic Sea island Heuwiese. During the study period, PCBs decreased significantly. Concentrations of PFOS ranged between 46 and 170 ng/g wet weight [ww] at Trischen, 39 to 99 ng/g ww at Mellum, and 20 to 159 ng/g ww at Heuwiese. Since 2000 and 2003, concentration levels decreased in eggs from Mellum and Heuwiese, respectively. Perfluorooctanoic acid was the dominant perfluorinated carboxylic acid in the North Sea eggs (Trischen 2.0 to 74 ng/g ww; Mellum 2.6 to 118 ng/g ww), whereas perfluoroundecanoate [PFUnA] and perfluorodecanoate [PFDA] (means 3.9 ± 3.6 ng/g and 2.9 ± 2.3 ng/g ww, respectively) dominated in the Baltic Sea eggs. At all three locations, longer-chained perfluorinated carboxylic acids (perfluorononanoate, PFDA, PFUnA, perfluorododecanoate) increased during the monitoring period. PBDE concentrations (sum of 35 congeners) in eggs were in the ranges of 282 to 2,059 ng/g lw (Mellum), 116 to 1,722 ng/g (Trischen), and 232 to 2,021 ng/g lw (Heuwiese). Congeners associated with commercial Penta- and Octa-BDE formulations decreased during the study period. No decrease was observed for technical Deca-BDE.

Conclusion

Effects of regulatory measures were apparent for PCBs and Penta- and Octa-BDE, while no consistent trend is noticeable for PFOS.     

Comparison of atrazine losses in three small headwater catchments

Understanding the processes causing herbicide transport to surface waters is crucial to determine mitigation options to reduce these losses. To this end, we investigated the atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) transport in three agricultural catchments (1.1-2.1 km2) in the watershed of Lake "Greifensee" (Switzerland). In 1999, atrazine application data were recorded for all three catchments. Time proportional samples were taken at a high temporal resolution at the catchment outlets. Extremely wet conditions caused large relative losses from the catchments, ranging between 0.6 and 3.5% of the amount applied. Most of the atrazine load was due to event-driven diffuse losses from the fields. Farmyard runoff contributed less but caused the highest concentrations (up to 31 microg L(-1)) in the brooks. The maximum concentrations due to diffuse losses varied between 1.2 and 8.2 microg L(-1) among the catchments. Despite different absolute concentration levels, the concentration time-series were very similar. It seems that the travel-times within the catchments were mainly controlled by the rainfall pattern with little influence of the catchment properties. These properties, however, caused the relative losses to vary by a factor of 6 between the catchments. This variability could be partly explained by differences in the connectivity of the fields to the brooks and by their hydrological soil properties. A comparison of the losses from the three catchments with those from the entire watershed of Lake Greifensee demonstrated that they were representative for the larger area. Hence, the study results provide a good data set to evaluate distributed models predicting herbicide losses.     

WATER QUALITY STRATIFICATION IN SHALLOW WASTEWATER STABILIZATION PONDS1

ABSTRACT: The physical limnology of three modern wastewater stabilization ponds serving a small community in Minnesota was investigated over a 1-year period (July 1989 - October 1990). Water temperatures and associated meteorological parameters were recorded continuously; underwater light, dissolved oxygen, pH, and Secchi depth were measured intermittently (about weekly). Measurements of nutrients and planktonic species were made by other investigators. Water quality stratification dynamics were studied by analyzing variations of water temperature, dissolved oxygen, and pH distributions with time and over depth. Intermittent stratification and mixing of the shallow waste stabilization ponds (1–2 m deep) were documented and related to weather. The strong response of the ponds to seasonal and daily weather variations was observed. Three types of pond stratification conditions have been identified: (1) completely mixed during consecutive day and night, (2) stratified during the day and well-mixed during the night, and (3) continuously stratified during day and night. A diurnal cycle of stratification dynamics was first noticed in late April and persisted through summer and into fall. Differences in light attenuation and hence temperature stratification and DO distribution between pond 1 (primary), pond 2 (second primary) and pond 3 (secondary) in the wastewater treatment system were documented and related to different waste loading conditions. Temperature stratification affects chemical, microbial, and planktonic processes in the ponds. Results presented in this paper can be used to provide guidance for water quality sampling in monitoring of pond performance. Information on true mixing conditions is also needed to gain better understanding of important factors affecting pond operation, and for process simulations and reactor modeling of waste stabilization ponds.     

OXYGEN DEMAND IN ICE COVERED LAKES AS IT PERTAINS TO WINTER AERATION1

ABSTRACT: Winterkill, the death of fish under ice due to oxygen deficiency, threatens hundreds of shallow lakes in the upper Midwest of the United States every winter. For decades, attempts have been made to prevent winterkill, usually through aeration, with mixed results. In large part, the failure of strategies to prevent winterkill can be linked to a lack of understanding of winter limnology and in particular, of oxygen dynamics under ice. Most winterkill lakes behave as closed systems with regard to oxygen. Consequently, the oxygen content of an ice and snow covered lake is essentially a function of the amount of initial storage and the rate of depletion. Should the stored oxygen be insufficient to prevent near anoxia before melting of the ice cover occurs, winterkill will result. Most oxygen consumption in ice covered lakes is due to bacterial respiration and chemical oxidation at the sediment/water interface, the remainder occurring in the water column. Oxygen consumption (and thus depletion) is a function of the velocity and oxygen concentration of the near sediment water. This is due to the fact that oxygen transport to the sediment is mediated by a diffusive boundary layer adjacent to the sediment surface. Winter oxygen depletion rates decrease when the oxygen concentration of the overlying water falls below about 3 mg/l. Aeration techniques which increase the oxygen concentration and velocity of the near-sediment water also increase the oxygen consumption (depletion) rate.     

SIDE EFFECTS OF 58 YEARS OF COPPER SULFATE TREATMENT OF THE FAIRMONT LAKES,MINNESOTA1

The shallow Fairmont Lakes in southern Minnesota have been treated with copper sulfate for 58 years to reduce excessive algal growth. Copper sulfate was applied to five lakes at cumulative rates upo to 1647 kg/ha (1470 1b/acre), totaling 1.5 million kilograms. Data collected since treatment of the Fairmont Lakes began in 1921 provide alarming insights into lake responses to sustained chemical treatment with copper sulfate. Short-term and long-term effects have occurred. Short-term effects include: a) the intended temporary killing of algae, b) dissolved oxygen depletion by decomposition of dead algae, c) accelerated phosphorus recycling from the lake bed and recovery of the algal population within 7 to 21 days, and d) occasional fish kills due to oxygen depletion or copper toxicity or both. Long-term effects are shown to include: a) copper accumulation in the sediments, b) tolerance adjustments of certain species of algae to higher copper sulfate dosages, c) shift of species from green to blue-green algae and from game fish to rough fish, d) disappearance of macrophytes, and e) reductions in benthic macroinvertebrates. The conclusion is that while copper sulfate treatments enjoy great popularity because they kill and remove algae almost instantaneously, other immediate or cumulative side effects can be harmful to many other aquatic organisms.     

Mass spectrometry up to 1 million mass units for the simultaneous detection of primary soot and of soot precursors (nanoparticles) in flames

A hybrid setup consisting of low pressure burner, flow reactor and photo-ionization mass spectrometer was used for the simultaneous detection of primary soot and of flame generated nanoparticles precursing soot. The studied flames were low pressure (120-180 mbar) C2H4/O2 flames surrounded by an N2 shield. The flow reactor was not used in this study. Through variation of the burner conditions (stoichiometry, sampling height) it could be shown that nanoparticles and soot are entirely independent species. The former, in particular, are found very early in the flame and their concentration profiles do not vary very much throughout the flame. This renders the possibility that nanoparticles are emitted together with soot and consequently may constitute an additional environmental hazard. Photo-ionization mass spectrometry is well suited for the detection of these particles.