Lead reduction and redistribution in the forest floor in New Hampshire northern hardwoods

Because of the affinity of organic matter for lead, atmospheric loadings of this pollutant have been strongly retained in the forest floor. With the regulation of Pb emissions, loadings have decreased. We measured changes in Pb in forest floor horizons at a variety of northern hardwood sites in New Hampshire from the late 1970s to the 1990s. In all seven of the sites in which horizons were distinguished within the forest floor, Pb was found to be declining in the upper (Oie) horizon, but not in the underlying Oa and A horizons. At the Hubbard Brook Experimental Forest (HBEF), this loss from the Oie resulted in a 36% loss of Pb from the forest floor as a whole between 1976 and 1997 (p < 0.001). In contrast, in six stands in the Bartlett Experimental Forest (BEF), losses of Pb averaging >50% from the Oi and Oe horizons (p = 0.01) between 1979 and 1994 were compensated by gains in the Oa and A horizons. Similarly, at seven additional stands in the White Mountain National Forest, changes in the forest floor as a whole from 1980 to 1995 were not statistically significant (redistribution within the forest floor was not evaluated at these sites). Lead concentrations were highest in the Oe or Oie in the 1970s, but were highest in the Oa horizon in the 1990s. There was no significant pattern of Pb loss or retention as a function of stand age across all the sites.     

Current issues and uncertainties in the measurement and modelling of air-vegetation exchange and within-plant processing of POPs

Air-vegetation exchange of POPs is an important process controlling the entry of POPs into terrestrial food chains, and may also have a significant effect on the global movement of these compounds. Many factors affect the air-vegetation transfer including: the physicochemical properties of the compounds of interest; environmental factors such as temperature, wind speed, humidity and light conditions; and plant characteristics such as functional type, leaf surface area, cuticular structure, and leaf longevity. The purpose of this review is to quantify the effects these differences might have on air/plant exchange of POPs, and to point out the major gaps in the knowledge of this subject that require further research. Uptake mechanisms are complicated, with the role of each factor in controlling partitioning, fate and behaviour process still not fully understood. Consequently, current models of air-vegetation exchange do not incorporate variability in these factors, with the exception of temperature. These models instead rely on using average values for a number of environmental factors (e.g. plant lipid content, surface area), ignoring the large variations in these values. The available models suggest that boundary layer conductance is of key importance in the uptake of POPs, although large uncertainties in the cuticular pathway prevents confirmation of this with any degree of certainty, and experimental data seems to show plant-side resistance to be important. Models are usually based on the assumption that POP uptake occurs through the lipophilic cuticle which covers aerial surfaces of plants. However, some authors have recently attached greater importance to the stomatal route of entry into the leaf for gas phase compounds. There is a need for greater mechanistic understanding of air-plant exchange and the 'scaling' of factors affecting it. The review also suggests a number of key variables that researchers should measure in their experiments to allow comparisons to be made between studies in order to improve our understanding of what causes any differences in measured data between sites.     

Destruction of Wetlands and Waterbird Populations by Dams and Irrigation on the Murrumbidgee River in Arid Australia

The Lowbidgee floodplain is the Murrumbidgee Rivers major wetland in southeastern Australia. From more than 300,000 ha in the early 1900s, at least 76.5% was destroyed (58%) or degraded (18%) by dams (26 major storages), subsequent diversions and floodplain development. Diversions of about 2,144,000 ML year^–1 from the Murrumbidgee River come from a natural median flow of about 3,380,000 ML year^–1 providing water for Australias capital, hydroelectricity, and 273,000 ha of irrigation. Diversions have reduced the amount of water reaching the Lowbidgee floodplain by at least 60%, from 1888 to 1998. About 97,000 ha of Lowbidgee wetland was destroyed by development of the floodplain for an irrigation area (1975–1998), including building of 394 km of channels and 2,145 km of levee banks. Over 19 years (1983–2001), waterbird numbers estimated during annual aerial surveys collapsed by 90%, from an average of 139,939 (1983–1986) to 14,170 (1998–2001). Similar declines occurred across all functional groups: piscivores (82%), herbivores (87%), ducks and small grebe species (90%), large wading birds (91%), and small wading birds (95%), indicating a similar decline in the aquatic biota that formed their food base. Numbers of species also declined significantly by 21%. The Lowbidgee floodplain is an example of the ecological consequences of water resource development. Yanga Nature Reserve, within the Lowbidgee floodplain, conserved for its floodplain vegetation communities, will lose these communities because of insufficient water. Until conservation policies adequately protect river flows to important wetland areas, examples such as the Lowbidgee will continue to occur around the world.     

Use of Remote Sensing Techniques to Determine the Effects of Grazing on Vegetation Cover and Dune Elevation at Assateague Island National Seashore: Impact of Horses

The effects of grazing by feral horses on vegetation and dune topography at Assateague Island National Seashore were investigated using color-infrared imagery, lidar surveys, and field measurements. Five pairs of fenced and unfenced plots (300 m²) established in 1993 on sand flats and small dunes with similar elevation, topography, and vegetation cover were used for this study. Color-infrared imagery from 1998 and field measurements from 2001 indicated that there was a significant difference in vegetation cover between the fenced and unfenced plot-pairs over the study period. Fenced plots contained a higher percentage of vegetation cover that was dominated by American beachgrass (Ammophila breviligulata). Lidar surveys from 1997, 1999, and 2000 showed that there were significant differences in elevation and topography between fenced and unfenced plot-pairs. Fenced plots were, on average, 0.63 m higher than unfenced plots, whereas unfenced plots had generally decreased in elevation after establishment in 1993. Results demonstrate that feral horse grazing has had a significant impact on dune formation and has contributed to the erosion of dunes at Assateague Island. The findings suggest that unless the size of the feral horse population is reduced, grazing will continue to foster unnaturally high rates of dune erosion into the future. In order to maintain the natural processes that historically occurred on barrier islands, much larger fenced exclosures would be required to prevent horse grazing.     

Effects of static vs. tidal hydrology on pollutant transformation in wetland sediments

This work addressed effects of hydrology on biogeochemical processes relevant to pollutant chemical transformation in wetland sediments. Microcosms were designed to impose three hydrologic conditions on salt marsh sediments: (i) drained-oxidized redox potenial (Eh); (ii) flooded-reduced Eh and, (iii) diurnal tide-oscillating Eh. The test chemicals were N- and/or S-heterocycles (NSHs) including quinoxaline (1,4-benzodiazine), 2-methylquinoxaline(2-methyl-1,4-benzodiazine), 2,3-dimethylquinoxalinen (2,3-dimethyl-1,4-benzodiazine), phenazine (2,3,5,6-dibenzo-1,4-diazine), acridine (2,3,5,6-dibenzopyridine), dibenzothiophene (2,3,5-dibenzothiophene), phenothiazine (dibenzo-1,4-thiazine), and phenanthridine (2,3-benzoisoquinoline). Biogeochemical processes reflected the hydrologic conditions in ways analogous to field settings, e.g., Eh characteristics were drastically different: static (flooded and drained) systems had reduced (mu = -428 mV +/- 57) and oxidized (mu = +73 mV +/- 32) values, respectively, with no evidence of periodic variation while the tidal systems exhibited regularly oscillating Eh (amplitudes 40-250 mV). Sediment trace gases also corresponded to the Eh, with the major species detected being CO2 and H2O (drained, tidal) vs. CO2 + H2O + sulfides + methane (flooded). The NSH transformation rates were different in each hydrologic regime and decreased as follows: tidal > or = drained > flooded. These results indicated that there were subtle differences in NSH processing in drained and tidal systems, but both of these systems transformed NSHs faster and to lower levels than flooded sediments. These data suggest that in situ remediation options that preserve wetland integrity and tidal hydrology can be as or more effective than static conditions that obtain in approaches such as impoundment and excavation-upland placement.     

Diuron occurrence and distribution in soil and surface and ground water associated with grass seed production

Little is known about the occurrence and distribution of the herbicide diuron [3-(3,4-dichlorophenyl)-1,1-dimethyl urea] in soil, ground water, and surface water in areas affected by grass-seed production. A field study was designed to investigate the occurrence and distribution of diuron and its transformation products at a poorly drained field site located along an intermittent tributary of Lake Creek in the southern Willamette Valley of Oregon. The experimental sites consisted of a field under commercial grass seed production with a cultivated riparian zone and a second site that was part of the same grass seed field but with a noncultivated riparian zone. Diuron and its transformation product DCPMU [3-(3,4-dichlorophenyl)-1-methylurea] were the only significant residues detected in this study. Concentrations of diuron in surface water declined from a maximum of 28 microg/L immediately following application to low levels that persisted as long as flow was present. Diuron and DCPMU concentrations in shallow ground water (15-36 cm below ground surface) were highest (2-13 microg/L) in the zone immediately adjacent (0.5 m) to Lake Creek and indicated the influence of stream water on shallow ground water near the stream. Diuron and DCPMU detected in soil prior to the second season's application indicated the persistence of diuron and DCPMU from the previous year's application. Surface runoff during the rainy season removes only a very small percentage (<1%) of the applied herbicide. In addition, no evidence was obtained for the downward transport of diuron or its transformation products to deep ground water.     

Components of the Total Water Balance of an Urban Catchment

A daily model was used to quantify the components of the total urban water balance of the Curtin catchment, Canberra, Australia. For this catchment, the mean annual rainfall was found to be three times greater than imported potable water, and the sum of the output from the separate stormwater and wastewater systems exceeded the input of imported potable water by some 50%. Seasonal and annual variations in climate exert a very strong influence over the relative magnitude of the water balance components; this needs to be accounted for when assessing the potential for utilizing stormwater and wastewater within an urban catchment.     

Response of Ceriodaphnia dubia to ionic silver: discrepancies among model predictions, measured concentrations and mortality

Silver thiosulfate, often a waste product of photoprocessing, is less bioavailable or toxic to aquatic organisms than is ionic silver. We conducted duplicate 48-h Ceriodaphnia dubia tests in reconstituted laboratory water using treatments of 92.7 nM Ag+ with various concentrations of thiosulfate. Expected Ag+ concentrations were generated for thiosulfate treatment levels using MINEQL + chemical equilibrium modeling. Ag+ concentrations in treatments were determined using a novel silicon-based sensor. Based on predicted Ag+ and published 48-h LC50 values for C. dubia, we did not expect to observe adverse effects. Yet, 100% mortality was observed at low thiosulfate treatments, whereas > 85% and > 95% survival was observed at higher thiosulfate treatment levels, respectively. Our results indicate that biotic responses match the sensor-based Ag+ concentrations. However, there is a discrepancy between these empirical results and responses expected to occur with Ag+ concentrations as predicted by MINEQL + chemical modeling. By correlating silicon sensor data with toxicity results obtained from our laboratory, our work clearly relates a specific chemical form (Ag+) to toxicity results.     

Soil testing to predict phosphorus leaching

Subsurface pathways can play an important role in agricultural phosphorus (P) losses that can decrease surface water quality. This study evaluated agronomic and environmental soil tests for predicting P losses in water leaching from undisturbed soils. Intact soil columns were collected for five soil types that a wide range in soil test P. The columns were leached with deionized water, the leachate analyzed for dissolved reactive phosphorus (DRP), and the soils analyzed for water-soluble phosphorus (WSP), 0.01 M CaCl2 P (CaCl2-P), iron-strip phosphorus (FeO-P), and Mehlich-1 and Mehlich-3 extractable P, Al, and Fe. The Mehlich-3 P saturation ratio (M3-PSR) was calculated as the molar ratio of Mehlich-3 extractable P/[Al + Fe]. Leachate DRP was frequently above concentrations associated with eutrophication. For the relationship between DRP in leachate and all of the soil tests used, a change point was determined, below which leachate DRP increased slowly per unit increase in soil test P, and above which leachate DRP increased rapidly. Environmental soil tests (WSP, CaCl2-P, and FeO-P) were slightly better at predicting leachate DRP than agronomic soil tests (Mehlich-1 P, Mehlich-3 P, and the M3-PSR), although the M3-PSR was as good as the environmental soil tests if two outliers were omitted. Our results support the development of Mehlich-3 P and M3-PSR categories for profitable agriculture and environmental protection; however, to most accurately characterize the risk of P loss from soil to water by leaching, soil P testing must be fully integrated with other site properties and P management practices.     

Coupled abiotic-biotic mineralization of 2,4,6-trinitrotoluene (TNT)

Munitions wastes such as TNT are widespread contaminants in soils and ground waters. We investigated a coupled abiotic-biotic treatment scheme for remediation of aqueous solutions of TNT. Mineralization of aqueous TNT (0.22 mM) was initially optimized with minimum reactant use (Fe3+ and H2O2) in light-assisted and dark, modified Fenton reactions at acidic and neutral pH. Complete TNT degradation occurred under all reaction conditions within 24 h. Using the optimum reactant concentrations, coupled abiotic-biotic reactions showed an increase in TNT mineralization, from 47 to 80%, after biomass addition to the acidic, dark Fenton-like reaction. Comparable increases of TNT mineralization were observed under neutral pH with similar reaction conditions. In light-assisted Fenton-like reactions at neutral pH, no increase in cumulative TNT mineralization (66%) was seen in coupled abiotic-biotic reactions. Abiotic photo-Fenton-like reactions alone, at acidic pH, produced complete TNT mineralization and required no biotic assistance. While light-enhanced Fenton reactions alone can provide high levels of TNT mineralization, the dark abiotic-biotic reaction scheme has perhaps a wider use due to a similar extent of TNT mineralization in the absence of light, leading to possible applications in soil slurry and in situ processes in the subsurface.