bluuebunny/crossref_metadata_2025 huggingface dataset:
Sources and Evolution of Anthropogenic Lead in Dated Sediments from Lake Clair, Québec, Canada
Authors: Ndzangou Sabary Omer , Richer‐Laflèche Marc , Houle Daniel
Published: May 2005

Two sediments cores were collected from the deepest part of Lake Clair (Québec, Canada) to assess the historical sources of Pb additions to the lake. The cores were collected by divers by carefully inserting a Plexiglas tube into the sediments. To determine the stratigraphic ages of the sediments, 210Pb and 137Cs activities were counted by γ‐ray spectroscopy. Lead concentrations and isotopic ratios were performed by inductively coupled plasma–mass spectrometry (ICP–MS), following digestion of the samples with a mixture of HF, HNO3, and HClO4 acids and Pb separation by anion‐exchange chromatography. Starting at the middle of the 19th century, Pb content of the sediments increased until 1975. The maximum Pb enrichment factor of 35 times (relative to the natural background) was found in sediments deposited in 1975. At this time, excess Pb flux was estimated to be about 0.03 g m−2 yr−1 Before 1872, the Pb isotopic ratios were relatively stable (mean 206Pb/207Pb = 1.20 ± 0.01), reflecting the natural Pb background. Between 1872 and 1894, the source of anthropogenic Pb was highly radiogenic as shown by the Pb isotopic signatures of the sediments (mean 206Pb/207Pb = 1.22 ± 0.01), possibly reflecting deforestation and agricultural developments in the St.‐Lawrence Valley. Between 1894 and 1937, widespread use of industrial and domestic charcoals may explain the isotopic composition of Pb accumulated in the sediments (mean 206Pb/207Pb = 1.19 ± 0.01). From 1937 to 1975, Pb isotopic compositions became less radiogenic (206Pb/207Pb from 1.18 to 1.17) even though elemental Pb abundance reached extremely high values (623 mg kg−1). This isotopic shift reflects increased use of alkyl‐lead in gasoline. For sediments accumulated between 1967 and 1996, the U.S. contribution to anthropogenic Pb accumulated in Lake Clair sediments amounted to between 30 and 63%.
Identification of the Source of Nitrate Contamination in Ground Water below an Agricultural Site, Jeungpyeong, Korea
Authors: Jun Seong‐Chun , Bae Gwang‐Ok , Lee Kang‐Kun , Chung Hyung‐Jae
Published: May 2005

This study applied hydrogeological characterization and isotope investigation to identify source locations and to trace a plume of ground water contaminated by nitrate. Most of the study site is agricultural fields with the remainder being residential. A poultry farm is also within the study area, so that potential point and nonpoint sources were present. Estimates of seasonal ground water recharge from irrigation and precipitation, leakage of sewage, and the regional ground water flow were linked to the seasonal changes in isotopic values. Ground water recharge largely occurred in spring and summer following precipitation or irrigation, depending on the locations. Natural and fertilized soils were identified as nonpoint sources of nitrate contamination in this area, while septic and animal wastes were identified as small point sources. The seasonal changes in the relative impact of these sources on ground water contamination were related to such factors as source distribution, the aquifer confining condition, precipitation rate, infiltration capacity, recharge rate, and the land use pattern.
Colloidal and Dissolved Phosphorus in Sandy Soils as Affected by Phosphorus Saturation
Authors: Ilg Katrin , Siemens Jan , Kaupenjohann Martin
Published: May 2005

Fertilization exceeding crop requirements causes an accumulation of phosphorus (P) in soils, which might increase concentrations of dissolved and colloidal P in drainage. We sampled soils classified as Typic Haplorthods from four fertilization experiments to test (i) whether increasing degrees of phosphorus saturation (DPS) increase concentrations of dissolved and colloidal P, and (ii) if critical DPS levels can be defined for P release from these soils. Oxalate‐extractable concentrations of P, iron (Fe), and aluminum (Al) were quantified to characterize DPS. Turbidity, zeta potential, dissolved P, and colloidal P, Fe, Al, and carbon (C) concentrations were determined in water and KCl extracts. While concentrations of dissolved P decreased with increasing depth, concentrations of water‐extractable colloidal P remained constant. In topsoils 28 ± 17% and in subsoils 94 ± 8% of water‐extractable P was bound to colloids. Concentrations of dissolved P increased sharply for DPS > 0.1. Colloidal P concentrations increased with increasing DPS because of an additional mobilization of colloids and due to an increase of the colloids P contents. In addition to DPS, ionic strength and Ca2+ affected the release of colloidal P. Hence, using KCl for extraction improved the relationship between DPS and colloidal P compared with water extraction. Accumulation of P in soils increases not only concentrations of dissolved P but also the risk of colloidal P mobilization. Leaching of colloidal P is potentially important for inputs of P into water bodies because colloidal P as the dominant water‐extractable P fraction in subsoils was released from soils with relatively low DPS.
Understanding Long‐Term Baseflow Water Quality Trends Using a Synoptic Survey of the Ground Water–Surface Water Interface, Central Wisconsin
Authors: Browne Bryant A. , Guldan Nathan M.
Published: May 2005

The relationship between stream water quality and landscape activities is difficult to evaluate where the principal source of stream flow is ground water seepage because the average travel time from ground water recharge areas to stream discharge positions can be on the order of decades. We tested the idea that past and future baseflow water quality can be predicted based on a synoptic survey of ground water recharge age‐dates (based on chlorofluorocarbon [CFC] measurements) and water quality measurements obtained at the ground water–surface water interface. In this study we (i) characterize the discharge‐weighted age distribution and water quality of ground water seepage into the Little Plover River (LPR); (ii) use this information to backcast and forecast baseflow NO3− concentrations; and (iii) evaluate NO3− backcasts against historical baseflow data (1960 to 2000). The discharge‐weighted apparent CFC age of ground water seepage into the LPR was 23.7 (±7) yr. Baseflow backcasts matched the four decade rise of baseflow NO3− from 2 to 8 mg L−1 Baseflow forecasts included three scenarios. Scenario A projects the historical rise of NO3− in the LPR basin's ground water recharge through 2050. Scenario B projects a leveling off of NO3− in ground water recharge in the year 2000. Scenario C projects a leveling off in the year 1985. Under Scenario A, LPR baseflow NO3− will increase steadily from 8 to 19 mg L−1 between 2000 and 2050. Under scenarios B and C baseflow NO3− will plateau at 13 mg L−1 in 2030 and at 10 mg L−1 in 2010, respectively. The approach developed in this study can be used to (i) reconstruct historical baseflow water quality patterns in the absence of long‐term monitoring data and (ii) project the effects of potential management decision on future water quality.
The Influence of Lipids on the Energetics of Uptake of Polycyclic Aromatic Hydrocarbons by Natural Organic Matter
Authors: Chilom Gabriela , Kohl Scott D. , Rice James A.
Published: May 2005

Although most of the organic carbon in soils and sediments may be composed of humic substances, their interaction with other compounds, especially their sorption interactions, may be significantly affected by the presence of small amounts of the other components of natural organic matter (NOM). In this investigation, the influence of the lipid fraction of NOM on the sorption thermodynamics of fluorene, phenanthrene, and pyrene to several geosorbent samples was examined before and after extraction of lipids. Batch experiments were performed at the same concentration for all polycyclic aromatic hydrocarbons (PAHs) (0.025 × their solubility in water) at different temperatures (10, 20, 30, and 40°C), and the thermodynamic parameters were calculated. Removal of the lipids increases the sorption capacity of the samples as well as the exothermicity of the process. The free energy change was negative for all the samples and no significant differences were noticed on lipid removal. The entropy changes were small and positive for the whole geosorbent samples, but even smaller or more negative when the lipids were removed. This indicates that the interaction of PAHs with soils and sediments in the absence of extractable lipids is stronger and the mechanisms involved may be different, changing from a partitioning‐like mechanism to specific adsorption. Because of the competition between lipids and PAHs for the same sorption sites, the lipids can be viewed as an “implicit sorbate.”
Multivariate Analysis of Paired Watershed Data to Evaluate Agricultural Best Management Practice Effects on Stream Water Phosphorus
Authors: Bishop Patricia L. , Hively W. Dean , Stedinger Jery R. , Rafferty Michael R. , Lojpersberger Jeffrey L. , Bloomfield Jay A.
Published: May 2005

Quantification of the effects of management programs on water quality is critical to agencies responsible for water resource protection. This research documents reductions in stream water phosphorus (P) loads resulting from agricultural best management practices (BMPs) implemented as part of an effort to control eutrophication of Cannonsville Reservoir, a drinking water supply for New York City. Dairy farms in the upstate New York reservoir basin were the target of BMPs designed to reduce P losses. A paired watershed study was established on one of these farms in 1993 to evaluate changes in P loading attributable to implementation of BMPs that included manure management, rotational grazing, and improved infrastructure. Intensive stream water monitoring provided data to calculate P loads from the 160‐ha farm watershed for all runoff events during a two‐year pre‐treatment period and a four‐year post‐treatment period. Statistical control for inter‐annual climatic variability was provided by matched P loads from a nearby 86‐ha forested watershed, and by several event flow variables measured at the farm. A sophisticated multivariate analysis of covariance (ANCOVA) provided estimates of both seasonal and overall load reductions. Statistical power and the minimum detectable treatment effect (MDTE) were also calculated. The results demonstrated overall event load reductions of 43% for total dissolved phosphorus (TDP) and 29% for particulate phosphorus (PP). Changes in farm management practices and physical infrastructure clearly produced decreases in event P losses measurable at the small watershed scale.
Tillage and Nutrient Source Effects on Water Quality and Corn Grain Yield from a Flat Landscape
Authors: Thoma David P. , Gupta Satish C. , Strock Jeffrey S. , Moncrief John F.
Published: May 2005

Beneficial effects of leaving residue at the soil surface are well documented for steep lands, but not for flat lands that are drained with surface inlets and tile lines. This study quantified the effects of tillage and nutrient source on tile line and surface inlet water quality under continuous corn (Zea maysL.) from relatively flat lands (<3%). Tillage treatments were either fall chisel or moldboard plow. Nutrient sources were either fall injected liquid hog manure or spring incorporated urea. The experiment was on a Webster–Canisteo clay loam (Typic Endoaquolls) at Lamberton, MN. Surface inlet runoff was analyzed for flow, total solids, NO3–N, NH4–N, dissolved P, and total P. Tile line effluent was analyzed for flow, NO3–N, and NH4–N. In four years of rainstorm and snowmelt events there were few significant differences (p< 0.10) in water quality of surface inlet or tile drainage between treatments. Residue cover minimally reduced soil erosion during both snowmelt and rainfall runoff events. There was a slight reduction in mineral N losses via surface inlets from manure treatments. There was also a slight decrease (p= 0.025) in corn grain yield from chisel‐plow plots (9.7 Mg ha−1) compared with moldboard‐plow plots (10.1 Mg ha−1). Chisel plowing (approximately 30% residue cover) alone is not sufficient to reduce nonpoint source sediment pollution from these poorly drained flat lands to the extent (40% reduction) desired by regulatory agencies.
A Method for Determining the Phosphorus Sorption Capacity and Amorphous Aluminum of Aluminum‐Based Drinking Water Treatment Residuals
Authors: Dayton E. A. , Basta N. T.
Published: May 2005

A high amorphous aluminum or iron oxide content in drinking water treatment residuals (WTRs) can result in a high phosphorus (P) sorption capacity. Therefore, WTR may be used beneficially to adsorb P and reduce P loss to surface or ground water. The strong relationship between acid ammonium oxalate–extractable aluminum (Alox) and Langmuir phosphorus adsorption maximum (Pmax) in WTR could provide a useful tool for determining Pmaxwithout the onus of the multipoint batch equilibrations necessary for the Langmuir model. The objectives of this study were to evaluate and/or modify an acid ammonium oxalate extraction of Aloxand the experimental conditions used to generate P adsorption isotherms to strengthen the relationship between Aloxand PmaxThe oxalate extraction solution to WTR ratio varied from 40:1, 100:1, and 200:1. Batch equilibration conditions were also varied. The WTR particle size was reduced from <2 mm to <150 μm, and batch equilibration was extended from 17 h to 6 d. Increasing the solution to WTR ratio to 100:1 extracted significantly greater Aloxat levels of >50 mg Al kg−1No additional increase was found at 200:1. Reducing WTR particle size from <2 mm to <150 μm increased Pmax2.46‐fold. Extending the equilibration time from 17 h to 6 d increased Pmaxby a mean of 5.83‐fold. The resulting empirical regression equation between the optimized Aloxand Pmax(r2= 0.91, significant at the 0.001 probability level) may provide a tool to estimate the Pmaxof Al‐based WTR simply by measuring AloxThe accurate determination of WTR Pmaxand Aloxis essential in using WTR effectively to reduce P loss in runoff or to reduce the solubility of P in agricultural soils or organic waste materials (biosolids, manure).
Distribution and Persistence of Pyrethroids in Runoff Sediments
Authors: Gan J. , Lee S. J. , Liu W. P. , Haver D. L. , Kabashima J. N.
Published: May 2005

Pyrethroids are commonly used insecticides in both agricultural and urban environments. Recent studies showed that surface runoff facilitated transport of pyrethroids to surface streams, probably by sediment movement. Sediment contamination by pyrethroids is of concern due to their wide‐spectrum aquatic toxicity. In this study, we characterized the spatial distribution and persistence of bifenthrin [BF; (2‐methyl(1,1′‐biphenyl)‐3‐yl)methyl 3‐(2‐chloro‐3,3,3‐trifluoro‐1‐propenyl)‐2,2‐dimethylcyclopropanecarboxylate] and permethrin [PM; 3‐(2,2‐dichloroethenyl)‐2,2‐dimethylcyclopropanecarboxylic acid (3‐phenoxyphenyl)methyl ester] in the sediment along a 260‐m runoff path. Residues of BF and PM were significantly enriched in the eroded sediment, and the magnitude of enrichment was proportional to the downstream distance. At 145 m from the sedimentation pond, BF was enriched by >25 times, while PM isomers were enriched by >3.5 times. Pesticide enrichment along the runoff path coincided with enrichment of organic carbon and clay fractions in the sediment, as well as increases in adsorption coefficient Kd, suggesting that the runoff flow caused selective transport of organic matter and chemical‐rich fine particles. Long persistence was observed for BF under both aerobic and anaerobic conditions, and the half‐life ranged from 8 to 17 mo at 20°C. The long persistence was probably caused by the strong pesticide adsorption to the solid phase. The significant enrichment, along with the prolonged persistence, suggests that movement of pyrethroids to the surface water may be caused predominantly by the chemically rich fine particles. It is therefore important to understand the fate of sediment‐borne pyrethroids and devise mitigation strategies to reduce offsite movement of fine sediment.
Advanced Thermal Characterization of Fractionated Natural Organic Matter
Authors: DeLapp Rossane C. , LeBoeuf Eugene J. , Chen Jie , Gu Baohua
Published: May 2005

This work focuses on an experimental investigation of the thermodynamic properties of natural organic matter (NOM), and whether fractions of NOM possess the same thermodynamic characteristics as the whole NOM from which they are derived. Advanced thermal characterization techniques were employed to quantify thermal expansion coefficients (α), constant‐pressure specific heat capacities (Cp), and thermal transition temperatures (Tt) of several aquatic‐ and terrestrial‐derived NOM. For the first time, glass transition behavior is reported for a series of NOM fractions derived from the same whole aquatic or terrestrial source, including humic acid–, fulvic acid–, and carbohydrate‐based NOM, and a terrestrial humin. Thermal mechanical analysis (TMA), standard differential scanning calorimetry (DSC), and temperature‐modulated differential scanning calorimetry (TMDSC) measurements revealed Tt ranging from −87°C for a terrestrial carbohydrate fraction to 62°C for the humin fraction. The NOM generally followed a trend of increasing Tt from carbohydrate to fulvic acid to humic acid to humin, and greater Tt associated with terrestrial fractions relative to aquatic fractions, similar to that expected for macromolecules possessing greater rigidity and larger molecular weight. Many of the NOM samples also possessed evidence of multiple transitions, similar to β and α transitions of synthetic macromolecules. The presence of multiple transitions in fractionated NOM, however, is not necessarily reflected in whole NOM, suggesting other potential influences in the thermal behavior of the whole NOM relative to fractionated NOM. Temperature‐scanning X‐ray diffraction studies of each NOM fraction confirmed the amorphous character of each sample through Tt
Initial Tree Establishment on Blocky Quarry Waste Ameliorated with Hydrogel or Slate Processing Fines
Authors: Rowe E. C. , Williamson J. C. , Jones D. L. , Holliman P. , Healey J. R.
Published: May 2005

Pocket planting reclamation techniques developed in the 1970s for revegetating blocky quarrying waste have met with very limited success, often because the low water‐holding capacity of the waste and limited root development within a small volume of planting pocket material result in severe drought mortality. We tested pocket planting approaches for waste tip reclamation at Europe's largest slate quarry, and compared materials for enhancing the continuity of water‐ and nutrient‐holding down into the interior of the waste tip. When small compost‐filled pocket planting bags were placed above slate processing fines (SPF) or water absorbent cross‐linked polyacrylamide gel (“hydrogel”), tree growth rates increased in comparison with pocket planting bags alone. The SPF significantly improved tree survival especially during severe drought, but survival was not enhanced by the use of hydrogel. The sorption characteristics of hydrogel indicated that its presence may help to reduce nutrient leaching, but that it may have a negative effect on nitrogen availability. A more likely explanation for the poor performance of pure hydrogel is that it did not maintain sufficient available water, because of discontinuities caused by shrinkage and movement of the hydrogel, and/or degradation of water‐holding capacity with environmental exposure. However, the root growth observed in the hydrogel treatments suggests that this technique, if adapted to reduce the effects of hydrogel shrinkage by using finer‐grade hydrogel, mixing it with other soil‐forming material, and reducing its exposure to extremes of temperature or sunlight, might have the potential to improve the growth and survival of trees planted on sites where delivery of heavy materials such as SPF is impractical. Fine mineral processing waste is freely available at active quarries and should be seen as a key resource for reclamation schemes.
Field‐Scale Application of Oily Food Waste and Nitrogen Fertilizer Requirements of Corn at Different Landscape Positions
Authors: Rashid M. T. , Voroney R. P.
Published: May 2005

Oily food waste (FOG; fat + oil + greases) containing high concentrations of fat, oil and grease is produced by the food service, production, and processing industries. It has a high C to N ratio (90:1) and can recycle soil available N through immobilization and remineralization during its decomposition. Experiments were conducted at a farm (Hillsburg fine sandy loam; Typic Hapludalf) having rolling topography (5 and 9% slope) during 1995 and 1996. Objectives of this study were to (i) examine the variability of available N and corn (Zea maysL.) grain yield at different landscape positions of FOG‐amended fields and (ii) determine whether N fertilizer management could be improved by considering the spatial variability of soil NO3–N at different landscape positions in FOG‐amended fields. A spatial and temporal variability in soil NO3–N was observed during both years. Corn grain yields at all N fertilizer application rates were affected by slope position and followed the pattern: lower > upper ≥ middle. Nitrogen fertilizer requirements for corn production in conjunction with FOG management were also affected by slope position. Essentially no additional fertilizer N was required for corn production at the lower landscape position. It was estimated that site‐specific fertilizer N management on FOG‐amended fields could result in an average savings of 51 and 63 kg N ha−1(with a potential economical savings of US$42 and US$52 ha−1) during 1995 and 1996, respectively.
Macroinvertebrate Communities in Agriculturally Impacted Southern Illinois Streams: Patterns with Riparian Vegetation, Water Quality, and In‐Stream Habitat Quality
Authors: Stone Mandy L. , Whiles Matt R. , Webber Jeremy A. , Williard Karl W. J. , Reeve John D.
Published: May 2005

Relationships between riparian land cover, in‐stream habitat, water chemistry, and macroinvertebrates were examined in headwater streams draining an agricultural region of Illinois. Macroinvertebrates and organic matter were collected monthly for one year from three intensively monitored streams with a gradient of riparian forest cover (6, 22, and 31% of riparian area). Bioassessments and physical habitat analyses were also performed in these three streams and 12 other nearby headwater streams. The intensively monitored site with the least riparian forest cover had significantly greater percent silt substrates than the sites with medium and high forest cover, and significantly higher very fine organics in substrates than the medium and high forested sites. Macroinvertebrates were abundant in all streams, but communities reflected degraded conditions; noninsect groups, mostly oligochaetes and copepods, dominated density and oligochaetes and mollusks, mostly Sphaerium and Physella, dominated biomass. Of insects, dipterans, mostly Chironomidae, dominated density and dipterans and coleopterans were important contributors to biomass. Collector–gatherers dominated functional structure in all three intensively monitored sites, indicating that functional structure metrics may not be appropriate for assessing these systems. The intensively monitored site with lowest riparian forest cover had significantly greater macroinvertebrate density and biomass, but lowest insect density and biomass. Density and biomass of active collector–filterers (mostly Sphaerium) decreased with increasing riparian forest. Hilsenhoff scores from all 15 sites were significantly correlated with in‐stream habitat scores, percent riparian forest, and orthophosphate concentrations, and multiple regression indicated that in‐stream habitat was the primary factor influencing biotic integrity. Our results show that these “drainage ditches” harbor abundant macroinvertebrates that are typical of degraded conditions, but that they can reflect gradients of conditions in and around these streams.
Bioproduction of Ferric Sulfate Used during Heavy Metals Removal from Sewage Sludge
Authors: Drogui Patrick , Mercier Guy , Blais Jean‐François
Published: May 2005

Toxic metals removal from wastewater sewage sludge can be achieved through microbial processes involving Acidithiobacillus ferrooxidans The oxidation of ferrous ions by A. ferrooxidans, cultured in sewage sludge filtrate, was studied in both batch and continuous flow stirred tank reactors. Sewage sludge filtrate containing natural nutrients (phosphorus and nitrogen) was recovered as effluent following the dehydration of a primary and secondary sludge mixture. Batch and continuous flow stirred tank reactor tests demonstrated that A. ferrooxidans were able to grow and completely oxidize ferrous iron in a culture medium containing more than 80% (v v−1) sewage sludge filtrate with 10 g Fe(II) L−1 added. Toxic levels were reached when total organic carbon in the sewage sludge filtrate exceeded 250 mg L−1 The ferric iron solution produced in the sludge filtrate by A. ferrooxidans was used to solubilize heavy metals in primary and secondary sludge. The solubilization of Cu, Cr, and Zn yielded 71, 49, and 80%, respectively. This is comparable with the yield percentages obtained using a FeCl3 solution. The cost of treating wastewater sewage sludge by bioproducing a ferric ion solution from sewage sludge is three times less expensive than the conventional method requiring a commercial ferric chloride solution.
Management Strategy Impacts on Ammonia Volatilization from Swine Manure
Authors: Panetta Diane M. , Powers Wendy J. , Lorimor Jeffery C.
Published: May 2005

Ammonia emitted from manure can have detrimental effects on health, environmental quality, and fertilizer value. The objective of this study was to measure the potential for reduction in ammonia volatilization from swine (Sus scrofa domestica) manure by temperature control, stirring, addition of nitrogen binder (Mohave yucca, Yucca schidigera Roezl ex Ortgies) or urease inhibitor [N‐(n‐butyl) thiophosphoric triamide (NBPT)], segregation of urine from feces, and pH modification. Swine manure [total solids (TS) = 7.6–11.2%, total Kjeldahl nitrogen (TKN) = 3.3–6.2 g/L, ammonium nitrogen ] was stored for 24, 48, 72, or 96 h in 2‐L polyvinyl chloride vessels. The manure was analyzed to determine pre‐ and post‐storage concentrations of TS and volatile solids (VS), TKN, and NH+4–N. The concentration of accumulated ammonia N in the vessel headspace (HSAN), post‐storage, was measured using grab sample tubes. Headspace NH3 concentrations were reduced 99.3% by segregation of urine from feces (P < 0.0001). Stirring and NBPT (152 μL/L) increased HSAN concentration (119 and 140%, respectively). Headspace NH3 concentration increased by 2.7 mg/m3 for every 1°C increase in temperature over 35°C. Slurry NH+4–N concentrations were reduced by segregation (78.3%) and acidification to pH 5.3 (9.4%), and increased with stirring (4.8%) and increasing temperature (0.06 g/L per 1°C increase in temperature over 35°C). Temperature control, urine–feces segregation, and acidification of swine manure are strategies with potential to reduce or slow NH+4–N formation and NH3 volatilization.
Persistence and Pathways of Testosterone Dissipation in Agricultural Soil
Authors: Lorenzen Angela , Chapman Ralph , Hendel John G. , Topp Edward
Published: May 2005

The persistence and pathways of dissipation of testosterone in three agricultural soils were examined in laboratory microcosm incubations at different soil moistures (1.7–39%) and temperatures (4–30°C) using 14C‐ and 3H‐labeled and unlabeled testosterone. Sterilized loam was also examined to assess possible abiotic pathways. Extractable 14C decreased rapidly for all three soils at 30°C with times to dissipate 50% of material (DT50) ranging from 8.5 to 21 h. Respired 14CO2 accounted for approximately 50% of the applied 14C after 120 h. Androgenic activity of soil extracts declined faster than the extractable 14C levels demonstrating that testosterone was not being converted to compounds with greater activity. Dissipation rates of nonvolatile, extractable 3H in loam at 7, 15, and 39% moisture were similar, but the rate in air‐dried loam (1.7% moisture) was significantly reduced. High performance liquid chromatography (HPLC) analysis of extracts of 14C‐testosterone‐treated loam incubated at 30°C for 6 h revealed that the 14C was distributed among the remaining testosterone and three major metabolites (4‐androstene‐3,17‐dione, 5α‐androstane‐3,17‐dione, and 1,4‐androstadiene‐3,17‐dione), which accounted for 48.7, 23.7, and 9.6% of the remaining 14C, respectively. Periodic analysis of soil incubated at 23, 12, and 4°C showed that the rates of testosterone dissipation and metabolite appearance and subsequent dissipation were temperature dependent with rates decreasing with decreasing temperature. In sterilized loam, 4‐androstene‐3,17‐dione was the only metabolite detected. We conclude that testosterone is rapidly and thoroughly biodegraded in agricultural soils under a range of conditions typical of a temperate growing season and thus is unlikely to pose a long‐term risk to adjacent aquatic environments.
Persistent Organic Pollutants in Source‐Separated Compost and Its Feedstock Materials—A Review of Field Studies
Authors: Brändli Rahel C. , Bucheli Thomas D. , Kupper Thomas , Furrer Reinhard , Stadelmann Franz X. , Tarradellas Joseph
Published: May 2005

Composting and the application of compost to the soil follow the principle of recycling and sustainability. Compost can also have a positive effect on physical, chemical, and biological soil parameters. However, little is known about the origin, concentration, and transformation of persistent organic pollutants (POPs) in compost. We therefore compiled literature data on some priority POPs in compost and its main feedstock materials from more than 60 reports. Our data evaluation suggests the following findings. First, median concentrations of Σ 16 polycyclic aromatic hydrocarbons (PAHs), Σ 6 polychlorinated biphenyls (PCBs), and Σ 17 polychlorinated dibenzo‐p‐dioxins and ‐furans (PCDD/Fs) were higher in green waste (1803, 15.6 μg/kg dry wt., and 2.5 ng international toxicity equivalent [I‐TEQ]/kg dry wt.) than in organic household waste (635, 14.6 μg/kg dry wt., and 2.2 ng I‐TEQ/kg dry wt.) and kitchen waste (not available [NA], 14.9 μg/kg dry wt., 0.4 ng I‐TEQ/kg dry wt.). The POP concentrations in foliage were up to 12 times higher than in other feedstock materials. Second, in contrast, compost from organic household waste and green waste contained similar amounts of Σ 16 PAHs, Σ 6 PCBs, and Σ 17 PCDD/Fs (1915, 39.8 μg/kg dry wt., and 9.5 ng I‐TEQ/kg dry wt., and 1715, 30.6 μg/kg dry wt., and 8.5 ng I‐TEQ/kg dry wt., respectively). Third, concentrations of three‐ring PAHs were reduced during the composting process, whereas five‐ to six‐ring PAHs and Σ 6 PCBs increased by roughly a factor of two due to mass reduction during composting. Σ 17 PCDD/Fs had accumulated by up to a factor of 14. Fourth, urban feedstock and compost had higher POP concentrations than rural material. Fifth, the highest concentrations of POPs were usually observed in summer samples. Finally, median compost concentrations of POPs were greater by up to one order of magnitude than in arable soils, as the primary recipients of compost, but were well within the range of many urban soils. In conclusion, this work provides a basis for the further improvement of composting and for future risk assessments of compost application.
Dairy Farm Effluent Effects on Urine Patch Nitrous Oxide and Carbon Dioxide Emissions
Authors: Clough Tim J. , Kelliher Francis M.
Published: May 2005

Dairy farm effluent (DFE) comprises animal feces, urine, and wash‐down water collected at the milking shed. This is collected daily during the milking season and sprayed onto grazed dairy pastures. Urine patches in grazed pastures make a significant contribution to anthropogenic N2O emissions. The DFE could potentially mitigate N2O emissions by influencing the N2O to dinitrogen (N2) ratio, since it contains water‐soluble carbon (WSC). Alternatively, DFE may enhance N2O emissions from urine patches. The application of DFE may also provide a substrate for the production of CO2 in pasture soils. The effects of DFE on the CO2 and N2O emissions from urine patches are unknown. Thus a laboratory experiment was performed where repeated DFE applications were made to repacked soil cores. Dairy farm effluent was applied at 0, 7, or 14 d after urine deposition. The urine was applied once on Day 0. Urine contained 15N‐enriched urea. Measurements of N2O, N2, and carbon dioxide (CO2) fluxes, soil pH, and soil inorganic N concentrations were made. After 43 d the DFE had not mitigated N2O fluxes from urine patches. A small increase in the N2O flux occurred from the urine‐treated soils where DFE was applied 1 wk after urine deposition. The amount of WSC applied in the DFE proved to be insignificant compared with the amount of soil C released as CO2 following urine application. The priming of soil C in urine patches has implications for the understanding of soil C processes in grazed pasture ecosystems and the budgeting of C within these ecosystems.
Green Roof Stormwater Retention
Authors: VanWoert Nicholaus D. , Rowe D. Bradley , Andresen Jeffrey A. , Rugh Clayton L. , Fernandez R. Thomas , Xiao Lan
Published: May 2005

Urban areas generate considerably more stormwater runoff than natural areas of the same size due to a greater percentage of impervious surfaces that impede water infiltration. Roof surfaces account for a large portion of this impervious cover. Establishing vegetation on rooftops, known as green roofs, is one method of recovering lost green space that can aid in mitigating stormwater runoff. Two studies were performed using several roof platforms to quantify the effects of various treatments on stormwater retention. The first study used three different roof surface treatments to quantify differences in stormwater retention of a standard commercial roof with gravel ballast, an extensive green roof system without vegetation, and a typical extensive green roof with vegetation. Overall, mean percent rainfall retention ranged from 48.7% (gravel) to 82.8% (vegetated). The second study tested the influence of roof slope (2 and 6.5%) and green roof media depth (2.5, 4.0, and 6.0 cm) on stormwater retention. For all combined rain events, platforms at 2% slope with a 4‐cm media depth had the greatest mean retention, 87%, although the difference from the other treatments was minimal. The combination of reduced slope and deeper media clearly reduced the total quantity of runoff. For both studies, vegetated green roof systems not only reduced the amount of stormwater runoff, they also extended its duration over a period of time beyond the actual rain event.
The Effect of Phosphogypsum on Greenhouse Gas Emissions during Cattle Manure Composting
Authors: Hao Xiying , Larney Francis J. , Chang Chi , Travis Greg R. , Nichol Connie K. , Bremer Eric
Published: May 2005

Phosphogypsum (PG), a by‐product of the phosphate fertilizer industry, reduces N losses when added to composting livestock manure, but its impact on greenhouse gas emissions is unclear. The objective of this research was to assess the effects of PG addition on greenhouse gas emissions during cattle feedlot manure composting. Sand was used as a filler material for comparison. The seven treatments were PG10, PG20, PG30, S10, S20, and S30, representing the rate of PG or sand addition at 10, 20, or 30% of manure dry weight and a check treatment (no PG or sand) with three replications. The manure treatments were composted in open windrows and turned five times during a 134‐d period. Addition of PG significantly increased electrical conductivity (EC) and decreased pH in the final compost. Total carbon (TC), total nitrogen (TN), and mineral nitrogen contents in the final composted product were not affected by the addition of PG or sand. From 40 to 54% of initial TC was lost during composting, mostly as CO2, with CH4 accounting for <14%. The addition of PG significantly reduced CH4 emissions, which decreased exponentially with the compost total sulfur (TS) content. The emission of N2O accounted for <0.2% of initial TN in the manure, increasing as compost pH decreased from alkaline to near neutral. Based on the total greenhouse gas budget, PG addition reduced greenhouse gas emissions (CO2–C equivalent) during composting of livestock manure by at least 58%, primarily due to reduced CH4 emission.
Immobilized Co/Rh Heterobimetallic Nanoparticle‐Catalyzed Pauson–Khand‐Type Reaction
Authors: Park Kang Hyun , Chung Young Keun
Published: May 2005

Co/Rh heterobimetallic nanoparticles were prepared from cobalt‐rhodium carbonyl clusters [Co2Rh2(CO)12 and Co3Rh(CO)12] and immobilized on charcoal. HR‐TEM revealed that the size of the heterobimetallic nanoparticles was ca. 2 nm and ICP‐AES analysis showed a 2 : 2 and a 3 : 1 cobalt‐rhodium stoichiometry (Co2Rh2 and Co3Rh1) in the heterobimetallic nanoparticles. The Co/Rh heterobimetallic nanoparticles immobilized on charcoal were used as a catalyst in the Pauson–Khand‐type reaction under 1 atm of CO. The catalytic reactivity was highly dependent upon the ratio of Co : Rh with the highest reactivity being observed when the ratio was 2 : 2 (Co2Rh2). The Co2Rh2 immobilized catalyst is quite an effective catalyst for intra‐ and intermolecular Pauson–Khand‐type reactions. When the immobilized Co2Rh2 catalyst was used as a catalyst in the Pauson–Khand‐type reaction in the presence of an aldehyde instead of carbon monoxide, the catalytic system was highly efficient. When the reaction was carried out in the presence of chiral diphosphines, ee values up to 87% were observed. The catalytic system can be reused at least five times in the presence of chiral diphosphines without loss of catalytic activity and enantioselectivity. The addition of Hg(0), a known heterogeneous catalyst poison, completely inhibits further catalysis. Thus, an environmentally friendly and sustainable process was developed.
Continuous Chirality Measure in Reaction Pathways of Ruthenium‐Catalyzed Transfer Hydrogenation of Ketones
Authors: Handgraaf Jan‐Willem , Reek Joost N. H. , Bellarosa Luca , Zerbetto Francesco
Published: May 2005

Here we report theoretical studies on the ruthenium‐catalyzed reduction of acetophenone (and 2‐hexanone) with the intent of understanding the relative roles of catalyst and substrate along the reaction path. Overall ten reaction pathways are examined. The first eight are for acetophenone: they arise from the presence of two catalysts, with the more enantioselective one labeled 1, and the poorer one labeled 2, multiplied by the two configurations that the metal center of the catalysts can assume, multiplied by the two approaches, Re‐ and Si‐side, of the substrate to the catalyst. Two pathways are examined for 2‐hexanone and entail the two approaches to the ketone of the more effective catalyst. Density functional theory calculations provide structures of the minima and transition states, which subsequently have been assessed with the “continuous chirality measure” model developed by Avnir and collaborators. The picture that emerges is that the asymmetric induction is due to the interplay between the organometallic system and the organic substrate. This is effective only for catalyst 1, which can interact effectively with acetophenone along only one in four of the reaction pathways, but not for 2 for which two out of four pathways are opened. For the hydrogenation of 2‐hexanone, the same catalyst 1 cannot produce enantiomeric excesses because the conformation of the substrate in the transition state induced by the catalyst has a relative low chirality.
Enantioenriched Calcium‐(R)‐5,5′,6,6′,7,7′,8,8′‐Octahydro‐BINOL (H8‐BINOL): An Efficient Catalyst for the Creation of a Quaternary Stereocenter#
Authors: Kumaraswamy G. , Jena Nivedita , Sastry M. N. V. , Padmaja M. , Markondaiah B.
Published: May 2005

An efficient catalyst for the creation of a quaternary stereocenter has been developed utilizing easily available, eco‐friendly CaCl2 and applied for enantioselective carbon‐carbon bond forming reactions. Among the surveyed ligands, it was found that (R)‐5,5′,6,6′,7,7′,8,8′‐octahydro‐BINOL‐Ca (2f) gave maximum ee (72%) with excellent yields.
Iridium Complex‐Catalyzed Cross‐Coupling Reaction of Terminal Alkynes with Internal Alkynes via CH Activation of Terminal Alkynes
Authors: Hirabayashi Tomotaka , Sakaguchi Satoshi , Ishii Yasutaka
Published: May 2005

The cross‐dimerization of an electron‐rich terminal alkyne with an electron‐deficient internal alkyne was promoted by an iridium complex to produce a 1 : 1 adduct in high regio‐ and stereoselectivities. This reaction was extended to various combinations of terminal alkynes with internal alkynes such as alkynyl esters and alkynyl aldehydes. The selectivity of the reaction was found to markedly depend on the ligands used. When dppe was used as a ligand, the 1 : 2 cross‐cyclotrimerization reaction took place to form substituted benzene derivatives. A plausible reaction path was suggested based on a labeling experiment. This reaction provides a method for the production of complicated enynes which are difficult to be prepared by conventional methods.
Cu(acac)2 Immobilized in Ionic Liquids: A Recoverable and Reusable Catalytic System for Aza‐Michael Reactions
Authors: Kantam M. Lakshmi , Neeraja V. , Kavita B. , Neelima B. , Chaudhuri Mihir K. , Hussain Sahid
Published: May 2005

Copper(II) acetylacetonate immobilized in ionic liquids efficiently catalyzes the aza‐Michael reaction of amines with α,β‐unsaturated carbonyl compounds to produce the corresponding β‐amino carbonyl compounds with great alacrity in excellent yields. The reactions are far more facile than those reported earlier. The recovered ionic liquid phase containing the copper catalyst can be reused for several cycles with consistent activity.
Ligand Descriptor Analysis in Nickel‐Catalysed Hydrocyanation: A Combined Experimental and Theoretical Study
Authors: Burello Enrico , Marion Philippe , Galland Jean‐Christophe , Chamard Alex , Rothenberg Gadi
Published: May 2005

The problem of choosing the ‘right chelating ligand’ for a homogeneously catalysed reaction is outlined. A model is introduced that combines mechanistic information and ligand descriptors. This model is used together with automated synthesis tools to study the structure‐activity relationship in a diverse set of forty‐two ligands, and extract information on active regions in the catalyst space. The concept is demonstrated on nickel‐catalysed hydrocyanation, using bidentate phosphine and phosphite ligands. The charge at the ligating atoms, the rigidity of the molecules, the steric crowding around the Ni atom, and the bite angle are found to be the most important descriptors. A comparison is made with literature hydrocyanation data and approaches for designing new homogeneous catalysts are discussed.
A Mechanistic Study on Alcohol Oxidations with Oxygen Catalysed by TPAP‐Doped Ormosils in Supercritical Carbon Dioxide
Authors: Campestrini Sandro , Carraro Massimo , Ciriminna Rosaria , Pagliaro Mario , Tonellato Umberto
Published: May 2005

The heterogeneous oxidation of various alcohols with oxygen catalysed by TPAP‐doped ormosils in scCO2 at 75 °C and 22.0 MPa has been studied in detail. Sol‐gel segregation of TPAP into the inner porosity of an organically modified silica (ormosil) xerogel along with the use of a reaction medium which does not dissolve the catalyst, prevents aggregation of oxidation‐inactive ruthenium derivatives without the need of chemical tethering. Thus, at least 140 TONs may be obtained in the oxidation of primary alcohols with the formation of aldehydes as sole reaction products. Investigation of the oxidation mechanism shows that the catalytic process exhibits a first‐order dependence on the amount of catalyst, a fractional order on the alcohol concentration and a negative order for oxygen pressures higher than 0.2 bar. Evidence is presented for an associative oxidation mechanism simultaneously involving TPAP, organic substrate and oxygen.
Click Chemistry: Copper Clusters Catalyse the Cycloaddition of Azides with Terminal Alkynes
Authors: Pachón Laura Durán , van Maarseveen Jan H. , Rothenberg Gadi
Published: May 2005

Air‐stable copper nanoclusters are good catalysts in the Cu(I)‐catalysed “click” cycloaddition of azides with terminal alkynes to give 1,4‐disubstituted 1,2,3‐triazoles. No additional base or reducing agent is required. The reaction kinetics using various copper catalyst types and the function of copper particles in this system are studied and discussed.
Highly Regio‐ and Diastereoselective Palladium‐Catalyzed Allylic Substitution. Synthesis of 3‐(2‐Aminobutylidene)‐ 4‐arylazetidin‐2‐ones
Authors: Cardillo Giuliana , Fabbroni Serena , Gentilucci Luca , Perciaccante Rossana , Tolomelli Alessandra
Published: May 2005

The palladium‐catalyzed benzylamine attack to a particular allylic moiety, the 3‐alkenyl‐3‐bromoazetidin‐2‐one is herein reported. This reaction shows interesting mechanistic aspects and allows us to introduce in one step and under high regio‐ and stereocontrol the amino function in the C3 side chain of non‐conventional β‐lactams, thus offering the opportunity for designing new potential glutamine syntethase inhibitors, such as Tabtoxin analogues.
Competitive Hydrogenation of Alkyl‐Substituted Arenes by Transition‐Metal Nanoparticles: Correlation with the Alkyl‐Steric Effect
Authors: Fonseca Gledison S. , Silveira Edson T. , Gelesky Marcos A. , Dupont Jairton
Published: May 2005

The influence of substituents on rate constants of the hydrogenation of monoalkylbenzenes by transition metal nanoparticles or by classical heterogeneous catalysts can be rationalized in terms of the Taft rule. A series of the initial reaction rate constants obtained from various competitive toluene/benzene and toluene/monoalkylbenzene hydrogenation experiments catalyzed by transition‐metal nanoparticles prepared in the presence of imidazolium ionic liquids or surfactants [Ir(0), Rh(0) and Ru(0)] or by classical heterogeneous catalysts (PtO2, Rh/C, Rh/Al2O3, Ru/C, Ru/Al2O3 and Pd/C) have been correlated with the Taft equation $\left( {\log {{k_B k_B } \over {k_A k_a }} = \rho E_s } \right)$. Satisfactory correlation coefficients (r) (between 0.96 and 0.99) and positive slopes (ρ) between 0.38 and 0.83 have been obtained. The results clearly show that the reaction constants for the alkyl‐substituents can be expressed by steric factors and are independent of any other non‐steric factors. It is suggested that bulky alkylbenzene substituents, for both transition metal nanoparticles and classical heterogeneous hydrogenation reactions, lower the overall hydrogenation rate, implying a more disturbed transition state compared to the initial state of the hydrogenation (in terms of the Horiuti–Polanyi mechanism). This competitive method is suitable for the estimation of the constant selectivity for couples of alkylbenzenes in which the difference in hydrogenation rates are very high and experimentally difficult to measure and also useful for the design of more selective “nano” and classical catalysts for hydrogenation reactions.
Homologation of Monoterpenoids into New Sesquiterpenoids via Tandem Isomerisation/Claisen Rearrangement Reactions with Three‐Component Ruthenium Catalysts, and Ru(methallyl)2(COD) Revealed by High Throughput Screening Techniques
Authors: Le Nôtre Jérôme , Touzani Rachid , Lavastre Olivier , Bruneau Christian , Dixneuf Pierre H.
Published: May 2005

A catalytic system B based on a ruthenium source Ru3(CO)12, a bulky imidazolinium salt and Cs2CO3 appears very efficient for the transformation of a 1,7‐diene into a γ,δ‐unsaturated aldehyde via tandem isomerisation/Claisen reactions. 1,6‐Dienes arising from the terpenoids menthone and myrtenal were selectively transformed into the corresponding unsaturated aldehydes with catalyst B. High throughput experiments were undertaken to evaluate other multicomponent catalysts: metal source/ligand/base for these tandem reactions. An unexpected catalyst was found to be Ru(methallyl)2(COD) which can operate without additional ligand or reagent.