Removal of perchlorate from contaminated waters using surfactant-modified zeolite

We investigated the potential of using surfactant (hexadecyltrimethylammonium)-modified zeolite (SMZ) as an inexpensive sorbent for removing perchlorate (ClO(4)(-)) from contaminated waters in the presence of competing anions. In batch systems, the presence of 10 mM OH(-) (i.e., pH 12), CO(3)(2-), Cl(-), or SO(4)(2-) had little effect on the sorption of ClO(4)(-) by SMZ, indicating that the sorption of ClO(4)(-) by SMZ was very selective. The presence of 10 mM NO(3)(-), however, reduced the sorption of ClO(4)(-) at low initial concentrations. The maximum sorption capacity for ClO(4)(-) by the SMZ remained relatively constant (40-47 mmol kg(-1)), in the absence or presence of the competing ions. In flow-through systems, ClO(4)(-) broke through the SMZ columns much later than other anions present in an artificial ground water. The affinity of the anions for SMZ followed the sequence of ClO(4)(-) > > NO(3)(-) > SO(4)(2-) > Cl(-). Perchlorate loading under dynamic flow-through conditions was 34 mmol kg(-1), somewhat less than the maximum loading of 40 to 47 mmol kg(-1) determined by the batch method. Less than 1% of previously sorbed ClO(4)(-) was leached out by ultra-pure water, by extraction fluid #1 of the standard toxicity characteristic leaching procedure (TCLP), or by a solution of 0.28 M Na(2)CO(3)/0.5 M NaOH. About 40% of the previously sorbed ClO(4)(-) was leached out from SMZ by a 0.5 M NO(3)(-) solution. The exchange of ClO(4)(-) with NO(3)(-) corroborated results of the batch tests where NO(3)(-) was shown to compete with ClO(4)(-) sorption.     

Transport and biodegradation of perchlorate in soils

Perchlorate (ClO4-) contamination of ground water and surface water is a widespread problem, particularly in the western United States. This study examined the effect of biodegradation on perchlorate fate and transport in soils. Solute transport experiments were conducted on two surface soils. Pulses of solution containing perchlorate and Br- were applied to saturated soil columns at steady state water flow. Perchlorate behaved like a nonreactive tracer in Columbia loam (coarse-loamy, mixed, superactive, nonacid, thermic Oxyaquic Xerofluvent) but was degraded in Yolo loam (fine-silty, mixed, superactive, nonacid, thermic Mollic Xerofluvent). Batch experiments demonstrated that perchlorate removal from solution in Yolo loam was caused by biodegradation. Other batch experiments with Yolo loam surface and subsurface soils, Columbia loam surface soil, and dredge tailings demonstrated that perchlorate biodegradation required anaerobic conditions, an adequate carbon source, and an active perchlorate-degrading microbial population. The sequential reduction of perchlorate and NO3- by an indigenous soil microbial community in Yolo loam batch systems was also studied. Nitrate reduction occurred much sooner than perchlorate reduction in soils that had not been previously exposed to perchlorate, but NO3- and perchlorate were simultaneously reduced in soils previously exposed to perchlorate. The results of this study have implications for in situ remediation schemes and for agricultural soils that have been contaminated by perchlorate-tainted irrigation water.     

Clonal differences in mercury tolerance, accumulation, and distribution in willow

This study was performed to investigate mercury (Hg) tolerance, accumulation, and translocation within the genus Salix for the potential use of this plant to remediate Hg-contaminated sites. Six clones of willow (Salix spp.) were tested on tolerance to Hg by treating plants grown in solution culture with 0 to 15 microM HgCl(2). Results showed that willow had a large variation in its sensitivity to Hg. However, the accumulation and translocation of Hg to shoots was similar in the eight tested willow clones as shown by cold vapor atomic absorption spectrometry analysis when plants were treated with 0.5 microM HgCl(2) in a nutrient solution. The majority of total Hg accumulated was localized to the roots, whereas only 0.45 to 0.62% of the total Hg accumulated via roots was translocated to the shoots. Thus, the root system is the main tissue of willow that accumulates Hg and the majority of the Hg in the root system (80%) was bound in the cell wall.     

Quantifying water savings from willow removal in Australian streams

Willows (Salix Spp.), while not endemic to Australia, form dense stands in many stream locations. Australia has been experiencing a long-term drought and potential water extraction by willows is considered a significant problem, although little global scientific evidence exists to support such concerns. The extent of willow occupation in Australian streams has been deemed large enough to warrant investigation of their evapotranspiration rates and quantification of potential water savings from willow removal. Willows situated in-stream (permanent water) and on stream banks (semi-permanent water) were monitored over three summers from August 2005 to May 2008 employing heat pulse velocity sap flux sensors and field measurement of water balance components. A comparative study of native riparian River Red Gum trees was also undertaken. Differences in transpiration flux rates between willows with permanent and semi-permanent access to water were substantial, with peak transpiration of 15.2 mm day(-1) and 2.3 mm day(-1) respectively. Water balance calculations over the three year period indicate that an average potential net water saving of 5.5 ML year(-1)ha(-1) of crown projected area is achievable by removal of in-stream willows with permanent access to water. On stream banks, replacement of willows with native riparian vegetation will have no net impact on site water balances. Results also indicate that under the influence of natural environmental events such as drought, heat stress and willow sawfly infestation, evapotranspiration rates from in-stream willows remain greater than that from open water. These results will have important implications in environmental management of willows and in future water resource allocation and planning in Australia.     

Vegetation succession and impacts of biointrusion on covers used to limit acid mine drainage

A cover with capillary barrier effects (CCBE) was constructed in 1998 on the abandoned Lorraine mine tailings impoundment to limit the generation of acid mine drainage. The Ministry of Natural Resources and Fauna of Quebec (MRNF) is responsible for the site and for all restoration works on it, including CCBE construction. The CCBE is made up of three layers: a 0.3-m layer of sand used as a support and capillary break layer; a moisture-retaining layer with a thickness of 0.5 m (this layer is constructed of a nonplastic silt); and a 0.3-m sand and gravel layer on top. The main objective of the CCBE is to maintain one (or more) of the layers at a high degree of water saturation to impede oxygen migration and acid generation. Vegetation succession on the Lorraine CCBE results in an improvement in soil conditions, leading to the installation of deep-rooted species, which could represent a risk to CCBE long-term performance. Hence, the characterization of vegetation succession is an important aspect of the monitoring strategy for the Lorraine CCBE. Species occurrence was documented, and depth of tree roots was measured by excavation on a regular basis. Eight functional groups of plants were identified; herbaceous plants were the most abundant ecological plant groups. Tree ring counts confirmed that tree colonization started the year of CCBE construction (1999). Of the 11 tree species identified, the most abundant were poplar (Populus spp.), paper birch (Betula payrifera Marsh.), black spruce (Picea mariana Mill.), and willow (Salix spp.). Significant differences in occurrence related to environmental conditions were observed for most functional groups. Root excavation showed that tree roots exceeded the depth of the protective layer and started to reach the moisture-retaining layer; in 2008, root average depth was 0.4 m and the maximal root depth was 1.7 m.     

A simulation experiment on the effectiveness of tree and pasture filter strips to remove NO3-N in lateral soil water flow

The impact of vegetative filter strips to reduce the delivery of nonpoint source pollutants from agricultural land to inland water systems is now recognized as an important element in overall agro-ecosystem management. A glasshouse experiment was undertaken to measure the effectiveness of tree (Eucalyptus camaldulensis Dehnh. and Casuarina cunninghamiana Mq.) and pasture filter strips to intercept lateral movement of NO(3)-N in soil water. Tree treatments retained significantly more NO(3)-N associated with shallow soil water movement (between the A and B soil horizons) than bare ground. Nitrate-N removal was not significantly different between trees and pasture, and among the tree treatments. However, uptake and accumulation of NO(3)-N by pastures was significantly (P < 0.001) greater than the trees. The average rates of N accumulation were 0.82 g m(-)(2) and 1.52 g m(-2) wk(-1) for the tree plots and the pasture plots, respectively. The experiment also showed that the efficiency of NO(3)-N removal from soil solutions by trees was greater when NO(3)-N concentrations were relatively higher in the soil (81.4% removal at 20 mg L(-1) compared to 68.1% at 10 mg L(-1)).     

Root penetration of sealing layers made of fly ash and sewage sludge

Fly ash and sewage sludge are suggested materials for constructing sealing layers covering mine tailings impoundments. Little is known, however, of their effect on vegetation or resistance to root penetration. We investigate: (i) the ability of different plant species to grow in sealing layers comprising fly ash and sewage sludge, (ii) the impact on plant growth of freshly hardened fly ash compared to aged and leached ash, and (iii) the plant stress response to fly ashes of different properties. A 6-mo greenhouse study using birch (Betula pendula Roth.), Scots pine (Pinus sylvestris L.), Kentucky bluegrass (Poa pratensis L.), and willow (Salix viminalis L.) demonstrated that no roots could grow into a compacted layer consisting only of ash, while a 6:4, ash-sludge mixture admitted roots into the upper part and a 1:9, ash-sludge mixture was totally penetrated (to 15 cm in depth) by roots of willow and Scots pine. Freshly hardened ash prevented root growth more effectively than aged ash did, as was observed in tests using reed canarygrass (Phalaris arundinacea L.) and pea (Pisum sativum L.). Furthermore, extracts of highly alkaline ash were more toxic to pea in a 48-h toxicity test than less alkaline ash was. However, stress responses to diluted ash extracts of lower pH, measured as enzyme capacities in dwarf bean (Phaseolus vulgaris L.), were more related to the metal and ion contents. Root penetration of sealing layers is most effectively prevented if little sewage sludge is added, and if ash of high alkalinity is chosen.     

Enhancing phytoextraction: the effect of chemical soil manipulation on mobility, plant accumulation, and leaching of heavy metals

For heavy metal-contaminated agricultural land, low-cost, plant-based phytoextraction measures can be a key element for a new land management strategy. When agents are applied into the soil, the solubility of heavy metals and their subsequent accumulation by plants can be increased, and, therefore, phytoextraction enhanced. An overview is given of the state of the art of enhancing heavy metal solubility in soils, increasing the heavy metal accumulation of several high-biomass-yielding and metal-tolerant plants, and the effect of these measures on the risk of heavy metal leaching. Several organic as well as inorganic agents can effectively and specifically increase solubility and, therefore, accumulation of heavy metals by several plant species. Crops like willow (Salix viminalis L.), Indian mustard [Brassica juncea (L.) Czern.], corn (Zea mays L.), and sunflower (Helianthus annuus L.) show high tolerance to heavy metals and are, therefore, to a certain extent able to use the surpluses that originate from soil manipulation. More than 100-fold increases of lead concentrations in the biomass of crops were reported, when ethylenediaminetetraacetic acid (EDTA) was applied to contaminated soils. Uranium concentrations could be strongly increased when citric acid was applied. Cadmium and zinc concentrations could be enhanced by inorganic agents like elemental sulfur or ammonium sulfate. However, leaching of heavy metals due to increased mobility in soils cannot be excluded. Thus, implementation on the field scale must consider measures to minimize leaching. So, the application of more than 1 g EDTA kg(-1) becomes inefficient as lead concentration in crops is not enhanced and leaching rate increases. Moreover, for large-scale applications, agricultural measures as placement of agents, dosage splitting, the kind and amount of agents applied, and the soil properties are important factors governing plant growth, heavy metal concentrations, and leaching rates. Effective prevention of leaching, breeding of new plant material, and use of the contaminated biomass (e.g., as biofuels) will be crucial for the acceptance and the economic breakthrough of enhanced phytoextraction.     

Effect of water table on willows grown in amended mine tailing

Survival and growth characteristics of two montane riparian willow species, Geyer willow (Salix geyeriana Andersson) and mountain willow (Salix monticola Bebb), grown in amended fluvial mine tailing were investigated in a greenhouse study. Willow stem cuttings were planted in lysimeters that simulated a 60-cm amended tailing profile with three static water depths (20, 40, and 60 cm) and a fluctuating water table for a total of four water table treatments. Species and water table treatments affected plant biomass and chemical composition of the soil and plant tissue. Mountain willow leaf, stem, and root biomass were 62, 95, and 164% greater, respectively, than for Geyer willow. Averaging across species, the fluctuating water table negatively affected leaf and stem biomass compared with the 20- and 60-cm water table treatments. Manganese was the only metal in plant tissue to strongly respond to water table treatments. Manganese concentrations in mountain willow leaf tissue were approximately twofold higher in the two most saturated water table treatments (20 cm and fluctuating) than in the least saturated water table treatment (60 cm). This trend was consistent with chemical analyses of the growth media, which reflected higher bioavailable Mn in the saturated tailing profile compared with the unsaturated profile. Results from this study indicate that mountain willow is a more vigorous and possibly more metal-tolerant species than Geyer willow when grown in amended mine tailing and that a fluctuating water table negatively affects willow growth.     

Accumulation of rare earth elements in corn after agricultural application

Using both pot and plot experiments, the dose-dependent accumulation of rare earth elements (REs) in corn (Zea mays L.) after application of an agricultural REs mixture was measured. In the pot experiment, the dose-dependent accumulation of REs in corn root and stem was observed, but it could not be detected in corn leaf under the dosage of 20 mg REs kg(-1) soil (oven-dry mass). The non-observed effect concentration (NOEC) for accumulation of REs in corn seedling with the pot experiment was 1.0 mg REs kg(-1). In the plot experiment, the dose-dependent accumulation was observed at an early stage after application of REs and the NOEC value of 32 mg REs m(-2) was obtained. At harvest, no dose-dependent accumulation of REs was observed in any part of the corn. These results can be confirmed by the fingerprinting analysis based on the differences between La to RE ratios in the REs mixture and in pot or plot soil. We observed that the plant shows no preference on individual RE and the results of fingerprinting indicated clearly the incorporation of exogenous REs in plant tissues, in a similar manner as that observed in the dose-dependent distribution of RE concentrations. The results indicated also a translocation process of REs from plant root to leaf when applied to soil or from leaf to root when applied to leaf. A homeostatic regulation mechanism for excessive uptake of REs in plants is suggested to regulate the concentrations of REs in the plant.     

Chloride effects on nitrogen dynamics in forested and suburban stream debris dams

Organic debris dams (accumulations of organic material) can function as "hotspots" of nitrogen (N) processing in streams. Suburban streams are often characterized by high flows that prevent the accumulation of organic debris and by elevated concentrations of solutes, especially nitrate (NO(3)(-)) and chloride (Cl(-)). In this study we (1) studied the effects of urbanization on the extent and characteristics of debris dams in large and small streams and (2) evaluated the effects of NO(3)(-) and Cl(-) on rates of N cycle processes in these debris dams. In some suburban streams debris dams were small and rare, but in others factors that reduce the effects of high stream flows fostered the maintenance of debris dams. Ambient denitrification enzyme activity (DEA) in these suburban and forested streams was positively correlated with stream NO(3)(-) concentrations. In laboratory microcosms, DEA in debris dam material from a forested reference stream was increased by NO(3)(-) additions. Chloride additions constrained the response of DEA to NO(3)(-) additions in material from the forested stream, but had no effect on DEA in material from streams with a history of high Cl(-) levels. Chloride additions changed the sign of net N mineralization from negative (consumption of inorganic N) to positive in debris dam material from the forested reference stream, but had no effect on net mineralization in material from streams with a history of exposure to Cl(-). Understanding the factors regulating the maintenance and N cycling activity of organic debris, and incorporating them into urban stream management plans could have important effects on N dynamics in suburban watersheds.     

Soil sulfur amendments suppress selenium uptake by alfalfa and Western wheatgrass

Selenium (Se) is a potential soil contaminant in many parts of the world where it can pose a health risk to livestock and wildlife. Phosphate ore mining in Southeast Idaho has resulted in numerous waste rock dumps revegetated with forages to stabilize the dumps and support grazing. Alfalfa (Medicago sativa L.), smooth brome (Bromus inermis Leyss.), and western wheat grass [Pascopyrum smithii (Rydb.) A. L?ve] are the dominant forage species on these lands. To demonstrate the feasibility of using sulfur (S) as a soil amendment to restrict plant Se uptake, 3 kg pots containing 50:50 w/w soil and waste shale were uniformly mixed with 0, 0.5, 1.0, or 2.0 Mg ha(-1) S as either elemental S or gypsum. Pots were seeded with alfalfa or western wheat grass. Dry mass and tissue Se were monitored over several clippings. Soils were sampled at the conclusion of the study and analyzed for water-soluble, oxalate-extractable, and total Se. Sulfur amendments as either elemental S or gypsum at 1.0 Mg ha(-1) or greater equally suppressed Se uptake over 60% in both forage species. Alfalfa accumulated more Se than western wheat grass. Plant removal via successive clippings resulted in lower tissue Se accumulation over time than the use of S soil amendments alone. Alfalfa-planted soils contained lower water-soluble and oxalate-extractable Se than did the non-planted controls while western wheat grass-planted soils contained lower water-soluble Se. Applying S to these shale-based soils may be an economically viable option for treating Se-impacted, revegetated lands.     

Uptake and release of cesium-137 by five plant species as influenced by soil amendments in field experiments

Phytoextraction field experiments were conducted on soil contaminated with 0.39 to 8.7 Bq/g of 137Cs to determine the capacity of five plant species to accumulate 137Cs and the effects of three soil treatments on uptake. The plants tested were redroot pigweed (Amaranthus retroflexus L. var. aureus); a mixture of redroot pigweed and spreading pigweed (A. graecizans L.); purple amaranth (A. cruteus L.) x Powell's amaranth (A. powellii S. Watson), referred to here as the amaranth hybrid; Indian mustard [Brassica juncea (L.) Czern.]; and cabbage (Brassica oleracea L. var. capitata). For control plants, the concentration ratios (CR) of 137Cs were greatest for redroot pigweed and the amaranth hybrid, with average CR values of 1.0 +/- 0.24 and 0.95 +/- 0.14, respectively. The lowest value was for Indian mustard at 0.36 +/- 0.10. The soil treatments included (i) application of NH4NO3 solution to the soil after plants had matured, (ii) addition of composted manure to increase organic matter content of the soil, (iii) combination of the manure and ammonium solution treatments, and (iv) controls. The ammonium solution gave little overall increase in accumulation of 137Cs. The use of composted manure also had little influence, but the combination of the composted manure with application of ammonium solutions had a distinctly negative effect on plant uptake of 137Cs. On average the fraction of 137Cs taken up from the soil was reduced by 57.4 +/- 1.2% compared with controls. This was the result of release of competing ions, primarily Ca, from the manure and was observed across all five plant species tested. The application of ammonium solution took place in the last two weeks before harvest. The reduction of plant 137Cs content, by addition of the ammonium solution, as it interacted with the manure, indicates that substantial quantities 137Cs can be released from the shoots of plants as a result of sudden changes in soil solution chemistry.     

Erosional Consequence of Saltcedar Control

Removal of nonnative riparian trees is accelerating to conserve water and improve habitat for native species. Widespread control of dominant species, however, can lead to unintended erosion. Helicopter herbicide application in 2003 along a 12-km reach of the Rio Puerco, New Mexico, eliminated the target invasive species saltcedar (Tamarix spp.), which dominated the floodplain, as well as the native species sandbar willow (Salix exigua Nuttall), which occurred as a fringe along the channel. Herbicide application initiated a natural experiment testing the importance of riparian vegetation for bank stability along this data-rich river. A flood three years later eroded about 680,000 m³ of sediment, increasing mean channel width of the sprayed reach by 84%. Erosion upstream and downstream from the sprayed reach during this flood was inconsequential. Sand eroded from channel banks was transported an average of 5 km downstream and deposited on the floodplain and channel bed. Although vegetation was killed across the floodplain in the sprayed reach, erosion was almost entirely confined to the channel banks. The absence of dense, flexible woody stems on the banks reduced drag on the flow, leading to high shear stress at the toe of the banks, fluvial erosion, bank undercutting, and mass failure. The potential for increased erosion must be included in consideration of phreatophyte control projects.     

Constitutive expression of a high-affinity sulfate transporter in Indian mustard affects metal tolerance and accumulation

The Stylosanthes hamata SHST1 gene encodes a high-affinity sulfate transporter located in the plasma membrane. In this study the S. hamata SHST1 gene was constitutively expressed in Indian mustard [Brassica juncea (L.) Czern.] to investigate its importance for tolerance and accumulation of various oxyanions that may be transported by SHST1 and for cadmium, which is detoxified by sulfur-rich compounds. The transgenic SHST1 lines SHST1-12C and SHST1-4C were compared with wild-type Indian mustard for tolerance and accumulation of arsenate, chromate, tungstate, vanadate, and cadmium. As seedlings the SHST1 plants accumulated significantly more Cd and W, and somewhat more Cr and V. The SHST1 seedlings were less tolerant to Cd, Mo, and V compared to wild-type plants. Mature SHST1 plants were less tolerant than wild-type plants to Cd and Cr. SHST1 plants accumulated significantly more Cd, Cr, and W in their roots than wild-type plants. In their shoots they accumulated significantly more Cr and somewhat more V and W. Shoot Cd accumulation was significantly lower than in wild-type, and As levels were somewhat reduced. Compared to wild-type plants, sulfur accumulation was enhanced in roots of SHST1 plants but not in shoots. Together these results suggest that SHST1 can facilitate uptake of other oxyanions in addition to sulfate and that SHST1 mediates uptake in roots rather than root-to-shoot translocation. Since SHST1 overexpression led to enhanced accumulation of Cr, Cd, V, and W, this approach shows some potential for phytoremediation, especially if it could be combined with the expression of a gene that confers enhanced metal translocation or tolerance.     

Are leaves that fall from imidacloprid-treated maple trees to control Asian longhorned beetles toxic to non-target decomposer organisms?

The systemic insecticide imidacloprid may be applied to deciduous trees for control of the Asian longhorned beetle, an invasive wood-boring insect. Senescent leaves falling from systemically treated trees contain imidacloprid concentrations that could pose a risk to natural decomposer organisms. We examined the effects of foliar imidacloprid concentrations on decomposer organisms by adding leaves from imidacloprid-treated sugar maple trees to aquatic and terrestrial microcosms under controlled laboratory conditions. Imidacloprid in maple leaves at realistic field concentrations (3-11 mg kg(-1)) did not affect survival of aquatic leaf-shredding insects or litter-dwelling earthworms. However, adverse sublethal effects at these concentrations were detected. Feeding rates by aquatic insects and earthworms were reduced, leaf decomposition (mass loss) was decreased, measurable weight losses occurred among earthworms, and aquatic and terrestrial microbial decomposition activity was significantly inhibited. Results of this study suggest that sugar maple trees systemically treated with imidacloprid to control Asian longhorned beetles may yield senescent leaves with residue levels sufficient to reduce natural decomposition processes in aquatic and terrestrial environments through adverse effects on non-target decomposer organisms.     

Effects of Soil Conditions on Survival and Growth of Black Willow Cuttings

Current streambank restoration efforts focus on providing bank stability, enhancing water quality, and improving woody habitat using native vegetation rather than traditional engineering techniques. However, in most cases harsh site conditions limit restoration success. A two-year field study was conducted at Twentymile Creek, in northern Mississippi, investigating edaphic factors governing the survival of black willow (Salix nigra) cuttings used for streambank restoration. Low height growth, above-ground biomass production, and average leaf area were observed in willow cuttings grown in plots subjected to moisture deficits. However, sediment texture emerged as the dominant factor determining willow post growth, health, and survival. Shoot biomass, leaf biomass, and total above-ground biomass were 15-, 10-, and 14-fold greater for large willow cuttings (posts) grown in plots with sandy sediments relative to those grown in plots with similar moisture and soil redox potential but with silt and clay sediments. Average leaf size, average leaf mass and specific leaf area were all lower in fine textured plots. Under moisture conditions present at our sites, coarse-grained sediment (sand) was more conducive to willow growth, biomass production, and survival than were fine-grained sediments (silt/clay). Our results strongly suggest that soil texture and moisture conditions can determine restoration success. Therefore, it is critical that site conditions are factored into the selection of project locations prior to the initiation of willow planting restoration projects.     

Structure of a forested urban park: Implications for strategic management

Informed management of urban parks can provide optimal conditions for tree establishment and growth and thus maximize the ecological and aesthetic benefits that trees provide. This study assesses the structure, and its implications for function, of the urban forest in Allan Gardens, a 6.1 ha downtown park in the City of Toronto, Canada, using the Street Tree Resource Analysis Tool for Urban Forest Managers (STRATUM). Our goal is to present a framework for collection and analysis of baseline data that can inform a management strategy that would serve to protect and enhance this significant natural asset. We found that Allan Garden’s tree population, while species rich (43), is dominated by maple (Acer spp.) (48% of all park trees), making it reliant on very few species for the majority of its ecological and aesthetic benefits and raising disease and pest-related concerns. Age profiles (using size as a proxy) showed a dominance of older trees with an inadequate number of individuals in the young to early middle age cohort necessary for short- to medium-term replacement. Because leaf area represents the single-most important contributor to urban tree benefits modelling, we calculated it separately for every park tree, using hemispheric photography, to document current canopy condition. These empirical measurements were lower than estimates produced by STRATUM, especially when trees were in decline and lacked full canopies, highlighting the importance of individual tree condition in determining leaf area and hence overall forest benefits. Stewardship of natural spaces within cities demands access to accurate and timely resource-specific data. Our work provides an uncomplicated approach to the acquisition and interpretation of these data in the context of a forested urban park.     

Distribution and speciation of metals in annual rings of black willow

Information on the spatial distribution and speciation of metals in nonhyperaccumulator plants is lacking. This study used synchrotron X-ray fluorescence (SXRF) compositional imaging to investigate the spatial distribution of Ni, Mn, Cu, Zn, and Fe in annual rings of black willow (Salix nigra L.) collected from a metal-contaminated area, and used X-ray absorption spectroscopy (XAS) to investigate Ni and Mn speciation in regions of the annual rings with elevated Ni concentrations. Annual rings were recollected in early 2003 from an individual known to be enriched with Ni from previous studies. Compositional imaging showed Ni and associated co-contaminants conservatively located in an annual ring. When compared with a corresponding photomicrograph, SXRF compositional images showed that metals were sharply constrained by the boundaries of the annual ring, indicating a sudden onset and cessation of uptake, and a lack of post-growth mobility of the metals. There was a particularly strong correlation between Ni and Mn in the metal-enriched annual ring (r = 0.8822), which suggested similar transport and binding behavior of these elements. X-ray absorption spectroscopy showed Ni and Mn to be present in the 2+ oxidation state. X-ray absorption near edge structure spectroscopy (XANES) fingerprinting of localized, highly Ni-enriched regions within the lumen of willow xylem vessels found similarities with Ni-pectic acid complexes, Ni-histidine, and NiSO4.     

Changes in flood-plain vegetation and land use along the Missouri River from 1826 to 1972

Changes in vegetation and land use since 1826 were evaluated along the 800 kilometer portion of the Missouri River flood-plain that extends across the State of Missouri using County Land Office Survey records for 1826 and aerial photos for 1937, 1958, and 1972. The combined results show a decline in flood-plain forest coverage from 76% in 1826 to 13% in 1972; cultivated land increased from 18% to 83% during the same time. Uncultivated-unforested areas increased from 6% in 1826 to 27% in 1937, then declined to 1% in 1972; these changes occurred coincident with extensive bank-stabilization and channelization activities initiated in 1912 by the U.S. Army Corps of Engineers. Riverbank stabilization activity since that time may account for the increased rate of decline in flood-plain forests from 0.25% per year between 1826 and 1937 to 1.6% per year between 1937 and 1972.The overall species composition of the 1826 flood-plain forests was found to be most similar to mature forest stands evaluated in 1972; similar frequencies in 1826 and 1972 occurred for hackberry (Celtis occidentalis; 80% in 1826, 83% in 1972), elm (Ulmus spp.; 80% and 83%), and sycamore (Platanus occidentalis; 57% and 50%). Pawpaw (Asimina triloba), found only in mature flood-plain forests in 1972, was recorded along 54% of the 1826 section lines.These combined data indicate (1) that pre-settlement flood-plain forests were extensive and included frequent, mature stands, (2) that in certain areas substantial portions of the flood-plain were in cultivation prior to extensive riverbank stabilization and channelization, and (3) that increased flood-plain forest clearing occurred coincident with increased bank-stabilization activities.