Showing papers in "Journal of Environmental Quality in 2005"

Trace element chemistry in residual-treated soil: key concepts and metal bioavailability.

Abstract: Trace element solubility and availability in land-applied residuals is governed by fundamental chemical reactions between metal constituents, soil, and residual components. Iron, aluminum, and manganese oxides; organic matter; and phosphates, carbonates, and sulfides are important sinks for trace elements in soil-residual systems. The pH of the soil-residual system is often the most important chemical property governing trace element sorption, precipitation, solubility, and availability. Trace element phytoavailability in residual-treated soils is often estimated using soil extraction methods. However, spectroscopic studies show that sequential extraction methods may not be accurate in perturbed soil-residual systems. Plant bioassay is the best method to measure the effect of residuals on phytoavailability. Key concepts used to describe phytoavailability are (i) the salt effect, (ii) the plateau effect, and (iii) the soil-plant barrier. Metal availability in soil from metal-salt addition is greater than availability in soil from addition of metal-containing residuals. Plant metal content displays plateaus at high residual loadings corresponding to the residual's metal concentration and sorption capacity. The soil-plant barrier limits transmission of many trace elements through the food chain, although Cd (an important human health concern) can bypass the soil-plant barrier. Results from many studies that support these key concepts provide a basis of our understanding of the relationship between trace element chemistry and phytoavailability in residual-treated soils. Research is needed to (i) determine mechanisms for trace element retention of soil-residual systems, (ii) determine the effect of residuals on ecological receptors and the ability of residuals to reduce ecotoxicity in metal-contaminated soil, and (iii) predict the long-term bioavailability of trace elements in soil-residual systems.

Green roof stormwater retention: effects of roof surface, slope, and media depth.

Abstract: 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.

Antibiotic uptake by plants from soil fertilized with animal manure.

Abstract: Antibiotics are commonly added to animal feed as supplements to promote growth of food animals. However, absorption of antibiotics in the animal gut is not complete and as a result substantial amounts of antibiotics are excreted in urine and feces that end up in manure. Manure is used worldwide not only as a source of plant nutrients but also as a source of organic matter to improve soil quality especially in organic and sustainable agriculture. Greenhouse studies were conducted to determine whether or not plants grown in manure-applied soil absorb antibiotics present in manure. The test crops were corn (Zea mays L.), green onion (Allium cepa L.), and cabbage (Brassica oleracea L. Capitata group). All three crops absorbed chlortetracycline but not tylosin. The concentrations of chlortetracycline in plant tissues were small (2-17 ng g -1 fresh weight), but these concentrations increased with increasing amount of antibiotics present in the manure. This study points out the potential human health risks associated with consumption of fresh vegetables grown in soil amended with antibiotic laden manures. The risks may be higher for people who are allergic to antibiotics and there is also the possibility of enhanced antimicrobial resistance as a result of human consumption of these vegetables.

Tillage and crop residue effects on soil carbon and carbon dioxide emission in corn-soybean rotations.

Abstract: Soil C change and CO2 emission due to different tillage systems need to be evaluated to encourage the adoption of conservation practices to sustain soil productivity and protect the environment. We hypothesize that soil C storage and CO2 emission respond to conservation tillage differently from conventional tillage because of their differential effects on soil properties. This study was conducted from 1998 through 2001 to evaluate tillage effects on soil C storage and CO2 emission in Clarion-Nicollet-Webster soil association in a corn [Zea mays L.]-soybean [Glycine max (L.) Merr.] rotation in Iowa. Treatments included no-tillage with and without residue, strip-tillage, deep rip, chisel plow, and moldboard plow. No-tillage with residue and strip-tillage significantly increased total soil organic C (TC) and mineral fraction C (MFC) at the 0- to 5- and 5- to 10-cm soil depths compared with chisel plow after 3 yr of tillage practices. Soil CO2 emission was lower for less intensive tillage treatments compared with moldboard plow, with the greatest differences occurring immediately after tillage operations. Cumulative soil CO2 emission was 19 to 41% lower for less intensive tillage treatments than moldboard plow, and it was 24% less for no-tillage with residue than without residue during the 480-h measurement period. Estimated soil mineralizable C pool was reduced by 22 to 66% with less intensive tillage treatments compared with moldboard plow. Adopting less intensive tillage systems such as no-tillage, strip-tillage, deep rip, and chisel plow and better crop residue cover are effective in reducing CO2 emission and thus improving soil C sequestration in a corn-soybean rotation.

Nitrogen mineralization from organic residues: research opportunities.

Abstract: Research on nitrogen (N) mineralization from organic residues is important to understand N cycling in soils. Here we review research on factors controlling net N mineralization as well as research on laboratory and field modeling efforts, with the objective of highlighting areas with opportunities for additional research. Among the factors controlling net N mineralization are organic composition of the residue, soil temperature and water content, drying and rewetting events, and soil characteristics. Because C to N ratio of the residue cannot explain all the variability observed in N mineralization among residues, considerable effort has been dedicated to the identification of specific compounds that play critical roles in N mineralization. Spectroscopic techniques are promising tools to further identify these compounds. Many studies have evaluated the effect of temperature and soil water content on N mineralization, but most have concentrated on mineralization from soil organic matter, not from organic residues. Additional work should be conducted with different organic residues, paying particular attention to the interaction between soil temperature and water content. One- and two-pool exponential models have been used to model N mineralization under laboratory conditions, but some drawbacks make it difficult to identify definite pools of mineralizable N. Fixing rate constants has been used as a way to eliminate some of these drawbacks when modeling N mineralization from soil organic matter, and may be useful for modeling N mineralization from organic residues. Additional work with more complex simulation models is needed to simulate both gross N mineralization and immobilization to better estimate net N mineralized from organic residues.

Pharmaceuticals and other organic chemicals in selected north-central and northwestern Arkansas streams.

Abstract: Recently, our attention has focused on the low level detection of many antibiotics, pharmaceuticals, and other organic chemicals in water resources. The limited studies available suggest that urban or rural streams receiving wastewater effluent are more susceptible to contamination. The purpose of this study was to evaluate the occurrence of antibiotics, pharmaceuticals, and other organic chemicals at 18 sites on seven selected streams in Arkansas, USA, during March, April, and August 2004. Water samples were collected upstream and downstream from the influence of effluent discharges in northwestern Arkansas and at one site on a relatively undeveloped stream in north-central Arkansas. At least one antibiotic, pharmaceutical, or other organic chemical was detected at all sites, except at Spavinaw Creek near Mayesville, Arkansas. The greatest number of detections was observed at Mud Creek downstream from an effluent discharge, including 31 pharmaceuticals and other organic chemicals. The detection of these chemicals occurred in higher frequency at sites downstream from effluent discharges compared to those sites upstream from effluent discharges; total chemical concentration was also greater downstream. Wastewater effluent discharge increased the concentrations of detergent metabolites, fire retardants, fragrances and flavors, and steroids in these streams. Antibiotics and associated degradation products were only found at two streams downstream from effluent discharges. Overall, 42 of the 108 chemicals targeted in this study were found in water samples from at least one site, and the most frequently detected organic chemicals included caffeine, phenol, para-cresol, and acetyl hexamethyl tetrahydro naphthalene (AHTN).

Nitrogen oxide and methane emissions under varying tillage and fertilizer management.

Abstract: Comprehensive assessment of the total greenhouse gas (GHG) budget of reduced tillage agricultural systems must consider emissions of nitrous oxide (N2O) and methane (CH4), each of which have higher global warming potentials than carbon dioxide (CO2). Tillage intensity may also impact nitric oxide (NO) emissions, which can have various environmental and agronomic impacts. In 2003 and 2004, we used chambers to measure N2O, CH4, and NO fluxes from plots that had been managed under differing tillage intensity since 1991. The effect of tillage on non-CO2 GHG emissions varied, in both magnitude and direction, depending on fertilizer practices. Emissions of N2O following broadcast urea (BU) application were higher under no till (NT) and conservation tillage (CsT) compared to conventional tillage (CT). In contrast, following anhydrous ammonia (AA) injection, N2O emissions were higher under CT and CsT compared to NT. Emissions following surface urea ammonium nitrate (UAN) application did not vary with tillage. Total growing season non-CO2 GHG emissions were equivalent to CO2 emissions of 0.15 to 1.9 Mg CO2 ha(-1) yr(-1) or 0.04 to 0.53 Mg soil-C ha(-1) yr(-1). Emissions of N2O from AA-amended plots were two to four times greater than UAN- and BU-amended plots. Total NO + N2O losses in the UAN treatment were approximately 50% lower than AA and BU. This study demonstrates that N2O emissions can represent a substantial component of the total GHG budget of reduced tillage systems, and that interactions between fertilizer and tillage practices can be important in controlling non-CO2 GHG emissions.

Occurrence and fate of pharmaceuticals and personal care products (PPCPs) in biosolids

Abstract: Each year, large quantities of pharmaceuticals and personal care products (PPCPs) are used worldwide. Once conveyed to wastewater treatment plants, PPCPs can remain unchanged or undergo partial or complete transformation during wastewater treatment processes before discharge into the environment via effluent and biosolids for land application. Biosolids can be a major sink for some PPCPs. Previous investigations have indicated that land application of biosolids may be a potential important route through which PPCPs enter the environment. However, no information is available on exactly how closely the concentrations of PPCPs in the environmental media are related to the land application of PPCP-containing biosolids. This paper reviews currently available information on the occurrence of PPCPs in biosolids, methods of analysis, the potential fate of PPCPs in biosolids-applied soils, and composting as a potential means for removal of PPCPs from biosolids.

Structural and sorption characteristics of adsorbed humic acid on clay minerals.

Abstract: Clay-humic complexes are commonly distributed in natural environments. They play very important roles in regulating the transport and retention of hydrophobic organic contaminants in soils and sediments. This study examined the structural changes of humic acid (HA) after adsorption by clay minerals and determined phenanthrene sorption by clay-humic complexes. Solid- and liquid-state 13C nuclear magnetic resonance (NMR), for the first time, provided direct evidence for HA fractionation during adsorption on mineral surfaces, that is, aliphatic fractions were preferentially adsorbed by clay minerals while aromatic fractions were left in the solution. The ratio of UV absorbance of HA at 465 and 665 nm (E4 to E6 ratio), which is related to aromaticity, corroborated with the NMR results. For both montmorillonite and kaolinite, adsorbed HA fractions had higher sorption linearity (N) and affinity (K(oc)) than the source HA. The K(oc) of adsorbed HA for the clay-humic complexes could be up to several times higher than that of the source HA. This large increase may be contributed by the low polarity of the bound HA. Moreover, for each mineral, the N values of adsorbed HA increased with increasing HA loading. It is believed that HA may develop a more condensed structure on mineral surface at lower HA loading level due to the stronger interactions between HA and mineral surface as a result of close contacts.

Methods for speciation of metals in soils: a review.

Abstract: The inability to determine metal species in soils hampers efforts to understand the mobility, bioavailability, and fate of contaminant metals in environmental systems, to assess health risks posed by them, and to develop methods to remediate metal contaminated sites. Fortunately, great strides have been made in the development of methods of species characterization and in their application to the analysis of particulates and mixtures of solid phases in physics, analytical chemistry, and materials science. This manuscript highlights a selection of the analytical methods available today offering the greatest promise, briefly describes the fundamental processes involved, examines their limitations, points to how they have been used in the environmental and geochemical literature, and offers some suggested research directions in the hope of stimulating further investigation into the application of these powerful tools to the problems outlined above.

Relating soil phosphorus to dissolved phosphorus in runoff: a single extraction coefficient for water quality modeling.

Abstract: Phosphorus transport from agricultural soils contributes to eutrophication of fresh waters. Computer modeling can help identify agricultural areas with high potential P transport. Most models use a constant extraction coefficient (i.e., the slope of the linear regression between filterable reactive phosphorus [FRP] in runoff and soil P) to predict dissolved P release from soil to runoff, yet it is unclear how variations in soil properties, management practices, or hydrology affect extraction coefficients. We investigated published data from 17 studies that determined extraction coefficients using Mehlich-3 or Bray-1 soil P (mg kg(-1)), water-extractable soil P (mg kg(-1)), or soil P sorption saturation (%) as determined by ammonium oxalate extraction. Studies represented 31 soils with a variety of management conditions. Extraction coefficients from Mehlich-3 or Bray-1 soil P were not significantly different for 26 of 31 soils, with values ranging from 1.2 to 3.0. Extraction coefficients from water-extractable soil P were not significantly different for 17 of 20 soils, with values ranging from 6.0 to 18.3. The relationship between soil P sorption saturation and runoff FRP (microgram L(-1)) was the same for all 10 soils investigated, exhibiting a split-line relationship where runoff FRP rapidly increased at P sorption saturation values greater than 12.5%. Overall, a single extraction coefficient (2.0 for Mehlich-3 P data, 11.2 for water-extractable P data, and a split-line relationship for P sorption saturation data) could be used in water quality models to approximate dissolved P release from soil to runoff for the majority of soil, hydrologic, or management conditions. A test for soil P sorption saturation may provide the most universal approximation, but only for noncalcareous soils.

Resuspension of sediment-associated Escherichia coli in a natural stream.

Abstract: In this study, a tracer bacteria was used to investigate the resuspension and persistence of sediment-associated bacteria in a small alluvial stream The study was conducted in Swan Creek, located within the Grand River watershed of Ontario, Canada A 11-m2 section of the bed was seeded with a strain of Escherichia coli resistant to nalidixic acid (E coli NAR) The survival, transport, and redistribution of the tracer bacteria within a 17-km river section downstream of the source cell was assessed for a 2-mo period following the introduction of the tracer bacteria This study has illustrated that enteric bacteria can survive in bed sediments for up 6 wk and that inactivation of the tracer bacteria resembled typical first-order decay Critical conditions for resuspension, as well as resuspension rates, of sediment-associated bacteria were determined for several storm events The critical shear stress for E coli NAR resuspension in Swan Creek ranged from 15 to 17 N m(-2), which is comparable with literature values for critical shear stresses for erosion of cohesive sediments Bacteria resuspension was primarily limited to the rising limb of storm hydrographs implying that a finite supply of sediment-associated bacteria are available for resuspension during individual storm events The information presented in this paper will further the development of representative microbial water quality models

Prediction of Zinc, Cadmium, Lead, and Copper Availability to Wheat in Contaminated Soils Using Chemical Speciation, Diffusive Gradients in Thin Films, Extraction, and Isotopic Dilution Techniques

Abstract: To predict the availability of metals to plants, it is important to understand both solution- and solid-phase processes in the soil, including the kinetics of metal release from its binding agent (ligand and/or particle). The present study examined the speciation and availability of Zn, Cd, Pb, and Cu in a range of well-equilibrated metal-contaminated soils from diverse sources using several techniques as a basis for predicting metal uptake by plants. Wheat (Triticum aestivum L.) was grown in 13 metal-contaminated soils and metal tissue concentrations (Zn, Cd, Pb, and Cu) in plant shoots were compared with total soil metal concentrations, total soluble metal, and free metal activities (pM2+) in soil pore waters, 0.01 M CaCl2–extractable metal concentrations, E values measured by isotope dilution, and effective metal concentrations, CE, measured by diffusive gradients in thin films (DGT). In the DGT technique, ions are dynamically removed by their diffusion through a gel to a binding resin, while E values represent the isotopically exchangeable (labile) metal pools. Free metal activities (Zn2+, Cd2+, and Pb2+) in soil pore waters were determined using a Donnan dialysis technique. Plant Zn and Cd concentrations were highly related to CE, while relationships for Zn and Cd with respect to the other measures of metals in the soils were generally lower, except for CaCl2–extractable Cd. These results suggest that the kinetically labile solid-phase pool of metal, which is included in the DGT measurement, played an important role in Zn and Cd uptake by wheat along with the labile metal in soil solution. Plant Pb concentrations were highly related to both soil pore water concentrations and CE, indicating that supply from the solid phase may not be so important for Pb. Predictions of Cu uptake by wheat from these soils by the various measures of Cu were generally poor, except surprisingly for total Cu.

Principles of Soil and Plant Water Relations

Abstract: Introducing a new hobby for other people may inspire them to join with you. Reading, as one of mutual hobby, is considered as the very easy hobby to do. But, many people are not interested in this hobby. Why? Boring is the reason of why. However, this feel actually can deal with the book and time of you reading. Yeah, one that we will refer to break the boredom in reading is choosing principles of soil and plant water relations as the reading material.

Science of odor as a potential health issue.

Abstract: Historically, unpleasant odors have been considered warning signs or indicators of potential risks to human health but not necessarily direct triggers of health effects. However, citizen complaints to public health agencies suggest that odors may not simply serve as a warning of potential risks but that odor sensations themselves may cause health symptoms. Mal-odors emitted from large animal production facilities and wastewater treatment plants, for example, elicit complaints of eye, nose, and throat irritation, headache, nausea, diarrhea, hoarseness, sore throat, cough, chest tightness, nasal congestion, palpitations, shortness of breath, stress, drowsiness, and alterations in mood. There are at least three mechanisms by which ambient odors may produce health symptoms. First, symptoms can be induced by exposure to odorants (compounds with odor properties) at levels that also cause irritation or other toxicological effects. That is, irritation--rather than the odor--is the cause of the health symptoms, and odor (the sensation) simply serves as an exposure marker. Second, health symptoms from odorants at non-irritant concentrations can be due to innate (genetically coded) or learned aversions. Third, symptoms may be due to a co-pollutant (such as endotoxin) that is part of an odorant mixture. Objective biomarkers of health symptoms must be obtained, however, to determine if health complaints constitute health effects. One industry that is receiving much attention, worldwide, related to this subject is concentrated animal production agriculture. Sustainability of this industry will likely necessitate the development of new technologies to mitigate odorous aerial emissions. Examples of such "environmentally superior technologies" (EST) developed under the initiative sponsored through agreements between the Attorney General of North Carolina and Smithfield Foods and Premium Standard Farms are described.

Oxytetracycline sorption to organic matter by metal-bridging.

Abstract: The sorption of oxytetracycline to metal-loaded ion exchange resin and to natural organic matter by the formation of ternary complexes between polyvalent metal cations and sorbent- and sorbate ligand groups was investigated. Oxytetracycline (OTC) sorption to Ca- and Cu-loaded Chelex-100 resin increased with increasing metal/sorbate ratio at pH 7.6 (OTC speciation: 55% zwitterion, 45% anion). Greater sorption to Cu- than Ca-loaded resin was observed, consistent with the greater stability constants of Cu with both the resin sites and with OTC. Oxytetracycline sorption to organic matter was measured at pH 5.5 (OTC speciation: 1% cation, 98% zwitterion, 1% anion). No detectable sorption was measured for cellulose or lignin sorbents that contain few metal-complexing ligand groups. Sorption to Aldrich humic acid increased from "clean" < "dirty" (no cation exchange pretreatment) < Al-amended < Fe(III)-amended clean humic acid with K(d) values of 5500, 32000, 48000, and 250000 L kg(-1) C, respectively. Calcium amendments of clean humic acid suggested that a portion of the sorbed OTC was interacting by cation exchange. Oxytetracycline sorption coefficients for all humic acid sorbents were well-correlated with the total sorbed Al-plus-Fe(III) concentrations (r(2) = 0.87, log-log plot), suggesting that sorption by ternary complex formation with humic acid is important. Results of this research indicate that organic matter may be an important sorbent phase in soils and sediments for pharmaceutical compounds that can complex metals by the formation of ternary complexes between organic matter ligand groups and pharmaceutical ligand groups.

Freeze-thaw effects on phosphorus loss in runoff from manured and catch-cropped soils

Abstract: Concern over nonpoint source P losses from agricultural lands to surface waters in frigid climates has focused attention on the role of freezing and thawing on P loss from catch crops (cover crops). This study evaluated the effect of freezing and thawing on the fate of P in bare soils, soils mixed with dairy manure, and soils with an established catch crop of annual ryegrass (Lolium multiflorum L.). Experiments were conducted to evaluate changes in P runoff from packed soil boxes (100 by 20 by 5 cm) and P leaching from intact soil columns (30 cm deep). Before freezing and thawing, total P (TP) in runoff from catch-cropped soils was lower than from manured and bare soils due to lower erosion. Repeated freezing and thawing significantly increased water-extractable P (WEP) from catch crop biomass and resulted in significantly elevated concentrations of dissolved P in runoff (9.7 mg L(-1)) compared with manured (0.18 mg L(-1)) and bare soils (0.14 mg L(-1)). Catch crop WEP was strongly correlated with the number of freeze-thaw cycles. Freezing and thawing did not change the WEP of soils mixed with manures, nor were differences observed in subsurface losses of P between catch-cropped and bare soils before or after manure application. This study illustrates the trade-offs of establishing catch crops in frigid climates, which can enhance P uptake by biomass and reduce erosion potential but increase dissolved P runoff.

Straining, Attachment, and Detachment of Cryptosporidium Oocysts in Saturated Porous Media

Abstract: Accurate knowledge of the transport and deposition behavior for pathogenic Cryptosporidium parvum oocysts is needed to assess contamination and protect water resources. Experimental and modeling studies were undertaken to examine the roles of attachment, detachment, and straining on oocyst transport and retention. Saturated column studies were conducted using Ottawa aquifer sands (U.S. Silica, Ottawa, IL) with median grain sizes of 710, 360, and 150 microm. Decreasing the median sand size tended to produce lower effluent concentrations, greater oocyst retention in the sand near the column inlet, and breakthrough of oocysts at later times. Oocyst transport data also exhibited concentration tailing. Mathematical modeling of the oocyst transport data using fitted first-order attachment and detachment coefficients provided a satisfactory description of the observed effluent concentration curves, but a poor characterization of the oocyst spatial distribution. Modeling of these data using an irreversible straining term that is depth dependent provided a better description of the oocyst spatial distribution, but could not account for the observed effluent concentration tailing or late breakthrough times. A more physically realistic description of the data was obtained by modeling attachment, detachment, and straining. The percentage of total oocysts retained by straining was estimated from effluent mass balance considerations to be 68% for 710-microm sand, 79% for 360-microm sand, and 87% for 150-microm sand. Straining coefficients were then selected to achieve these percentages of total oocyst retention, and attachment and detachment coefficients were fitted to the effluent concentration curves. Dramatic differences in the predicted oocyst breakthrough curves were observed at greater transport distances for the various model formulations (inclusion or exclusion of straining). Justification for oocyst straining was provided by trends in the transport data, simulation results, pore size distribution information, and published literature.

Antibacterial activity of soil-bound antibiotics.

Abstract: There is some concern that antibiotic residues in land-applied manure may promote the emergence of antibiotic resistant bacteria in the environment. The goal of this study was to determine whether or not soil bound antibiotics are still active against bacteria. The procedure involved sorbing various amounts of tetracycline or tylosin on two different textured soils (Webster clay loam [fine-loamy, mixed, superactive, mesic Typic Endoaquolls] and Hubbard loamy sand [sandy, mixed, frigid Entic Hapludolls]), incubating these soils with three different bacterial cultures (an antibiotic resistant strain of Salmonella sp. [Salmonella(R)], an antibiotic sensitive strain of Salmonella sp. [Salmonella(S)], and Escherichia coli ATCC 25922), and then enumerating the number of colony forming units relative to the control. Incubation was done under both static and dynamic conditions. Soil-adsorbed antibiotics were found to retain their antimicrobial properties since both antibiotics inhibited the growth of all three bacterial species. Averaged over all other factors, soil adsorbed antimicrobial activity was higher for Hubbard loamy sand than Webster clay loam, most likely due to higher affinity (higher clay content) of the Webster soil for antibiotics. Similarly, there was a greater decline in bacterial growth with tetracycline than tylsoin, likely due to greater amounts of soil-adsorbed tetracycline and also due to lower minimum inhibitory concentration of most bacteria for tetracycline than tylosin. The antimicrobial effect of tetracycline was also greater under dynamic than static growth conditions, possibly because agitation under dynamic growth conditions helped increase tetracycline desorption and/or increase contact between soil adsorbed tetracycline and bacteria. We conclude that even though antibiotics are tightly adsorbed by clay particles, they are still biologically active and may influence the selection of antibiotic resistant bacteria in the terrestrial environment.

Surface runoff and transport of sulfonamide antibiotics and tracers on manured grassland.

Abstract: Despite their common use in animal production the environmental fate of the veterinary sulfonamide antibiotics after excretion is only poorly understood. We performed irrigation experiments to investigate the transport of these substances with surface runoff on grassland. Liquid manure from pigs treated with sulfadimidine was spiked with sulfadiazine, sulfathiazole, the herbicide atrazine (2-chloro-4-ethyl-amino-6-isopropylamino-1,3,5-triazine), and the conservative tracer bromide and spread onto eight plots. Four plots received the same amounts of the spiked substances in aqueous solution (controls). Apart from the application matrix we varied the time between application and irrigation. Manure increased the runoff volume up to six times compared with the controls. It seemed that manure enhanced the runoff by sealing the soil surface. On manured plots the relative antibiotic concentrations in runoff were higher than on the controls, reaching an average of 0.3% (sulfadiazine), 0.8% (sulfathiazole), and 1.4% (sulfadimidine) of the input concentrations after a 1-d contact time. The corresponding values on the controls were 0.16% for sulfadiazine and 0.08% for sulfathiazole. After 3 d, the maximum values on the manured plots were even higher, whereas they had fallen below the limit of quantification on the controls. As a consequence, the sulfonamide losses were 10 to 40 times larger on the manured plots. The relative mobility of the sulfonamides on the control plots followed the trend expected from their chromatographic separation but the opposite was found on the manured plots. Hence it is important to consider explicitly the physical and chemical effects of manure when assessing the environmental fate of sulfonamides.

Distribution and persistence of pyrethroids in runoff sediments.

Abstract: 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 K(d), 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 degrees 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.

Multivariate analysis of paired watershed data to evaluate agricultural best management practice effects on stream water phosphorus.

Abstract: 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.

Soil water repellency induced by long-term irrigation with treated sewage effluent.

Abstract: This study describes soil water repellency developed under prolonged irrigation with treated sewage effluent in a semiarid environment. Soil surface layer (0-5 cm) and soil profile (0-50 cm) transects were sampled at a high resolution at the close of the irrigation season and rainy winter season. Samples from 0- to 5-cm transects were subdivided into 1-cm slices to obtain fine scale resolution of repellency and organic matter distribution. Extreme to severe soil water repellency in the 0- to 5-cm soil surface layer persisted throughout the 2-yr study period in the effluent-irrigated Shamouti orange [Citrus sinensis (L.) Osbeck cv. Shamouti] orchard plot. Nearby Shamouti orange plots irrigated with tap water were either nonrepellent or only somewhat repellent. Repellency was very variable spatially and with depth, appearing in vertically oriented "repellency tongues." Temporal and spatial variability in repellency in the uppermost 5-cm soil surface layer was not related to seasonality, soil moisture content, or soil organic matter content. Nonuniform distribution of soil moisture and fingered flow were observed in the soil profile after both seasons, demonstrating that the repellent layer had a persistent effect on water flow in the soil profile. A lack of correlation between bulk density and volumetric water content in the soil profile demonstrates that the observed nonuniform spatial distribution of moisture results from preferential flow and not heterogeneity in soil properties. Soil water repellency can adversely affect agricultural production, cause contamination of underlying ground water resources, and result in excessive runoff and soil erosion.

Phosphorus losses from agricultural areas in river basins: effects and uncertainties of targeted mitigation measures.

Abstract: In this paper we show the quantitative and relative importance of phosphorus (P) losses from agricultural areas within European river basins and demonstrate the importance of P pathways, linking agricultural source areas to surface water at different scales. Agricultural P losses are increasingly important for the P concentration in most European rivers, lakes, and estuaries, even though the quantity of P lost from agricultural areas in European catchments varies at least one order of magnitude ( 2.1 kg P ha(-1)). We focus on the importance of P for the implementation of the EU Water Framework Directive and discuss the benefits, uncertainties, and side effects of the different targeted mitigation measures that can be adopted to combat P losses from agricultural areas in river basins. Experimental evidence of the effects of some of the main targeted mitigation measures hitherto implemented is demonstrated, including: (i) soil tillage changes, (ii) treatment of soils near ditches and streams with iron to reduce P transport from source areas to surface waters, (iii) establishment of buffer zones for retaining P from surface runoff, (iv) restoration of river-floodplain systems to allow natural inundation of riparian areas and deposition of P, and (v) inundation of riparian areas with tile drainage water for P retention. Furthermore, we show how river basin managers can map and analyze the extent and importance of P risk areas, exemplified by four catchments differing in size in Norway, Denmark, and the Netherlands. Finally, we discuss the factors and mechanisms that may delay and/or counteract the responses of mitigation measures for combating P losses from agricultural areas when monitored at the catchment scale.

A thermodynamically based method to quantify true sorption hysteresis.

Abstract: Sorption of organic chemicals to soils and sediments often shows true hysteresis (i.e., nonsingularity of the sorption-desorption isotherm not attributable to known experimental artifacts). Since true sorption hysteresis is fundamentally important to contaminant fate, a way to quantify it is desirable. Previously proposed indices of hysteresis are empirical and usually depend on the isotherm model. True sorption hysteresis to synthetic and natural organic solids has been attributed to irreversible alteration of the solid during the sorption-desorption cycle. Given this mechanism, we propose the Thermodynamic Index of Irreversibility (TII) for quantifying hysteresis in soils where natural organic matter dominates the sorption process. The TII is based on the difference in free energy between the real desorption state and the hypothetical fully reversible state. The index is 0 for completely reversible systems and approaches 1 as the process tends toward complete irreversibility. It does not require any assumptions about the physical properties or molecular composition of the solid, and it does not depend on a specific equilibrium model. A sensitivity analysis of measurement errors provides general recommendations for the setup of sorption-desorption experiments. The TII was applied to sorption of 1,4-dichlorobenzene (DCB) to two high-organic soils, Pahokee peat (PP) and Amherst soil (AS), and a low-rank coal reference material, Beulah-Zap lignite (BZL). Common artificial causes of hysteresis were eliminated. Hysteresis was significant in the peat and the coal. The TII was clearly concentration dependent for both solids; it decreased with concentration for the peat, but increased with concentration for the coal. The TII allows quantification of hysteresis as a function of sorbate-sorbent combination, concentration, time, and other variables.

A method for determining the phosphorus sorption capacity and amorphous aluminum of aluminum-based drinking water treatment residuals.

Abstract: 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 (Al(ox)) and Langmuir phosphorus adsorption maximum (P(max)) in WTR could provide a useful tool for determining P(max) without 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 Al(ox) and the experimental conditions used to generate P adsorption isotherms to strengthen the relationship between Al(ox) and P(max). The 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 50 mg Al kg(-1). No additional increase was found at 200:1. Reducing WTR particle size from <2 mm to <150 microm increased P(max) 2.46-fold. Extending the equilibration time from 17 h to 6 d increased P(max) by a mean of 5.83-fold. The resulting empirical regression equation between the optimized Al(ox) and P(max) (r(2) = 0.91, significant at the 0.001 probability level) may provide a tool to estimate the P(max) of Al-based WTR simply by measuring Al(ox). The accurate determination of WTR P(max) and Al(ox) is 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).

Sorption, mobility, and transformation of estrogenic hormones in natural soil.

Abstract: concentrated feedlot operations can enter surface wa- a pH of 7.9, a specific surface area of 1.51 10 5 m 2 kg 1 ters and result in hormone concentrations that could (Cihacek and Bremner, 1979), and a particle size distribution adversely affect aquatic health. The potency and poten- of 10% sand, 64% silt, and 26% clay (Gee and Bauder, 1986). tial for widespread contamination are the major con- All the physical soil properties, except specific surface, were cerns regarding hormones in the environment. Some determined at the Soil and Water Environmental Laboratory studies have shown that 17-estradiol concentrations of at North Dakota State University. The soil was prepared for 1 to 7 ng L 1 can significantly increase vitellogenin the column and batch experiments by air drying and sieving production in female painted turtles (Chrysemys picta) with a 2-mm sieve.

Nitrate Losses in Subsurface Drainage from a Corn–Soybean Rotation as Affected by Fall and Spring Application of Nitrogen and Nitrapyrin

Abstract: Substantial amounts of NO3 from agricultural crop production systems on poorly drained soils can be transported to surface water via subsurface drainage. A field study was conducted from the fall of 1993 through 2000 on a tile-drained Canisteo clay loam soil (fine-loamy, mixed, superactive, calcareous, mesic Typic Endoaquoll) to determine the influence of fall vs. spring application of N and nitrapyrin [NP; 2-chloro-6-(trichloromethyl) pyridine] on NO3 losses from a corn (Zea mays L.)-soybean [Glycine max (L.) Merr.] rotation. Four anhydrous ammonia treatments (fall N, fall N + NP, spring preplant N, and spring N + NP) were replicated four times and applied at 135 kg N ha(-1) for corn on individual drainage plots. Drainage occurred in all seven years. Seventy-one percent of the annual drainage and 75% of the annual NO3 loss occurred in April, May, and June. Fifty-four percent of the NO3 lost in the drainage occurred during the corn phase and 46% during the soybean phase. Annual flow-weighted NO3-N concentrations for the fall, fall + NP, spring, and spring + NP treatments averaged 14.3, 11.5, 10.7, and 11.3 mg L(-1) during the corn phase but annual NO3-N concentrations were still > or =10 mg L(-1) in three of six years for the spring preplant treatment. Averaged across the six rotation cycles, flow-normalized NO3-N losses ranked in the order: fall N > spring N + NP > fall N + NP > spring N. Under these conditions, NO3 losses in subsurface drainage from a corn-soybean rotation can be reduced 14% by spring N and 10% by late fall N + NP compared with fall-applied N. Nitrate losses were not appreciably reduced by adding NP to spring preplant N.

Nitrate losses in subsurface drainage from a corn-soybean rotation as affected by fall and spring application of nitrogen and nitrapyrin. [Erratum: 2003 Nov-Dec, v. 32, no. 6, p. 2447.]

Abstract: Substantial amounts of NO3 from agricultural crop production systems on poorly drained soils can be transported to surface water via subsurface drainage. A field study was conducted from the fall of 1993 through 2000 on a tile-drained Canisteo clay loam soil (fine-loamy, mixed, superactive, calcareous, mesic Typic Endoaquoll) to determine the influence of fall vs. spring application of N and nitrapyrin [NP; 2-chloro-6-(trichloromethyl) pyridine] on NO3 losses from a corn (Zea mays L.)-soybean [Glycine max (L.) Merr.] rotation. Four anhydrous ammonia treatments (fall N, fall N + NP, spring preplant N, and spring N + NP) were replicated four times and applied at 135 kg N ha(-1) for corn on individual drainage plots. Drainage occurred in all seven years. Seventy-one percent of the annual drainage and 75% of the annual NO3 loss occurred in April, May, and June. Fifty-four percent of the NO3 lost in the drainage occurred during the corn phase and 46% during the soybean phase. Annual flow-weighted NO3-N concentrations for the fall, fall + NP, spring, and spring + NP treatments averaged 14.3, 11.5, 10.7, and 11.3 mg L(-1) during the corn phase but annual NO3-N concentrations were still > or =10 mg L(-1) in three of six years for the spring preplant treatment. Averaged across the six rotation cycles, flow-normalized NO3-N losses ranked in the order: fall N > spring N + NP > fall N + NP > spring N. Under these conditions, NO3 losses in subsurface drainage from a corn-soybean rotation can be reduced 14% by spring N and 10% by late fall N + NP compared with fall-applied N. Nitrate losses were not appreciably reduced by adding NP to spring preplant N.

Long-Term Effects of Poultry Litter, Alum-Treated Litter, and Ammonium Nitrate on Phosphorus Availability in Soils

Abstract: Alum (Al2(SO4)314H2O) additions to poultry litter result in lower ammonia (NH3) volatilization and phosphorus (P) runoff; however, the long-term effects of alum on soil P behavior have been unknown. The objectives of this study were to evaluate the long-term effects of poultry litter, alum-treated litter, and ammonium nitrate (NH4NO3 )o n P availability in soils and P runoff. Two studies were initiated in 1995: a smallplot(1.533.0m)studyandapairedwatershed(0.405ha)study.In the small plot study 13 treatments (control, four rates of normal litter, fourratesofalum-treatedlitter,andfourratesofNH4NO3)wereapplied to tall fescue (Festuca arundinacea Schreb.) plots. Results show that after 7 yr water-extractable P (WEP) in surface soil samples was greater withnormallitter, butMehlichIIIPwasgreaterinsurfacesoils fertilized withalum-treatedlitter.Whensoilsamplesweretakenatdepthintervals to 50 cm in Year 7, Mehlich III P was only greater in the surface 5 cm for soils fertilizedwithalum-treatedlitter. AtlowerdepthsMehlichIII P was greater with normal litter, and WEP was up to 288% greater when normal litter was used, indicating that alum significantly reduced P leaching. Uptake of P by fescue was not affected by alum. Results from