Photochemistry and photoinduced toxicity of acifluorfen, a diphenyl-ether herbicide

Photochemistry studies can be helpful in assessing the environmental fate of chemicals. Photochemical reactions lead to the formation of by-products that can exhibit different toxicological properties from the original compound. For this reason the photochemical behavior of the herbicide acifluorfen (5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid) in the presence of different solvents was studied. Photochemical reactions were carried out using a high-pressure mercury arc and a solar simulator. Kinetic parameters and quantum yields were determined. The identification of photoproducts was performed by mass spectrometry and [1H] nuclear magnetic resonance (NMR). Nitrofluorfen, hydroxy-nitrofluorfen, 2-chloro-4-(trifluoromethyl)phenol, 5-trifluoromethyl-5'-nitrodibenzofuran, and other derivatives were identified. The photochemical reactions were also carried out in the presence of either a singlet or a triplet quencher, and in the presence of either a radical initiator or a radical inhibitor. Substances used as inhibitors of the excited levels T1 and S1 showed that photodegradation of acifluorfen begins from a singlet state S1 through a pi,pi* transition. The role of free radicals in the photodegradation of acifluorfen was determined and a radical mechanism was proposed. Toxicity tests against Daphnia magna Strauss showed that acifluorfen was not toxic at a concentration of 0.1 mM; however, photoproducts formed after 36 h of UV exposure of the herbicide induced a remarkable toxicity to the test organism.     

Pilot-scale treatment of RDX-contaminated soil with zerovalent iron

Soils in Technical Area 16 at Los Alamos National Laboratory (LANL) are severely contaminated from past explosives testing and research. Our objective was to conduct laboratory and pilot-scale experiments to determine if zerovalent iron (Fe(0)) could effectively transform RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) in two LANL soils that differed in physicochemical properties (Soils A and B). Laboratory tests indicated that Soil A was highly alkaline and needed to be acidified [with H2SO4, Al2(SO4)3, or CH3COOH] before Fe(0) could transform RDX. Pilot-scale experiments were performed by mixing Fe(0) and contaminated soil (70 kg), and acidifying amendments with a high-speed mixer that was a one-sixth replica of a field-scale unit. Soils were kept unsaturated (soil water content = 0.30-0.34 kg kg(-1)) and sampled with time (0-120 d). While adding CH3COOH improved the effectiveness of Fe(0) to remove RDX in Soil A (98% destruction), CH3COOH had a negative effect in Soil B. We believe that this difference is a result of high concentrations of organic matter and Ba. Adding CH3COOH to Soil B lowered pH and facilitated Ba release from BaSO4 or BaCO3, which decreased Fe(0) performance by promoting flocculation of humic material on the iron. Despite problems encountered with CH3COOH, pilot-scale treatment of Soil B (12 100 mg RDX kg(-1)) with Fe(0) or Fe(0) + Al2(SO4)3 showed high RDX destruction (96-98%). This indicates that RDX-contaminated soil can be remediated at the field scale with Fe(0) and soil-specific problems (i.e., alkalinity, high organic matter or Ba) can be overcome by adjustments to the Fe(0) treatment.     

ACCUMULATION OF AS,NI, CU,AND PB IN RETENTION AND RECHARGE BASINS SOILS FROM URBAN RUNOFF1

ABSTRACT: The accumulation of arsenic, nickel, copper, and lead in the soil profile was determined beneath five urban storm-water retention/recharge basins used by the Fresno Metropolitan Flood Control District, California. Soils were sampled from the surface to the first zone of saturation and compared with soils from an adjacent un-contaminated control site. These elements were found to be accumulating in the first few centimeters of basin soil and are important to the effectiveness of a specific best management practice, i.e., the retention and recharge of urban storm water. Study basins in use since 1962, 1965, and 1969 had lead contents in the 0–2 cm soil depth interval‘of 570, 670, and 1400 mg Pb/kg soil, respectively. The median indigenous soil lead concentration was 4.6 mg/kg soil. The practice of removing excess flood runoff water from two basins by pumping apparently is a factor in reducing the accumulation rate of these elements in the surface soils of the basins.     

Forest restoration potentials of coal-mined lands in the eastern United States

The Appalachian region in the eastern United Sates is home to the Earth's most extensive temperate deciduous forests, but coal mining has caused forest loss and fragmentation. More than 6000 km in Appalachia have been mined for coal since 1980 under the Surface Mining Control and Reclamation Act (SMCRA). We assessed Appalachian areas mined under SMCRA for forest restoration potentials. Our objectives were to characterize soils and vegetation, to compare soil properties with those of pre-SMCRA mined lands that were reforested successfully, and to determine the effects of site age on measured properties. Soils were sampled and dominant vegetation characterized at up to 10 points on each of 25 post-SMCRA mines. Herbaceous species were dominant on 56%, native trees on 24%, and invasive exotics on 16% of assessed areas. Mean values for soil pH (5.8), electrical conductivity (0.07 dS m(-1)), base saturation (89%), and coarse fragment content (50% by mass) were not significantly different from measured levels on the pre-SMCRA forested sites, but silt+clay soil fraction (61%) was higher, bicarbonate-extractable P (4 mg kg(-1)) was lower, and bulk density (1.20 g cm(-1)) was more variable and often unfavorable. Pedogenic N and bicarbonate-extractable P in surface soils increased with site age and with the presence of weathered rocks among coarse fragments. Our results indicate a potential for many of these soils to support productive forest vegetation if replanted and if cultural practices, including temporary control of existing vegetation, soil density mitigation, and fertilization, are applied to mitigate limitations and aid forest tree reestablishment and growth.     

Ecotoxic effect of phenanthrene on nitrifying bacteria in soils of different properties

Information on ecotoxicity of organic contaminants, such as polycyclic aromatic hydrocarbons (PAHs), in terrestrial environment is needed for establishing soil quality criteria and for risk assessment purposes. An ecotoxic effect of a model PAH compound (phenanthrene) toward soils microorganisms (nitrifying bacteria) was evaluated in 50 different soils. The soil samples were collected from agricultural land in four regions of Poland with varying levels of industrialization (Slaskie, Dolnoslaskie, Podlaskie, and Lubelskie voievodeships). Soils were characterized for basic physicochemical properties (texture, organic matter content, pH(KCl), total nitrogen content, total sorption capacity) and the content of contaminants including PAHs (73-800 microg kg(-1)), Pb (6-720 mg kg(-1)), and Zn (9-667 mg kg(-1)). Ecotoxicity of phenanthrene (applied at 10, 100, 500, and 1000 mg kg(-1)) to soils microorganisms was evaluated in laboratory studies in control conditions (incubation of soils for 7 d at 20 +/- 2 degrees C). Nitrification potential was used as the ecotoxicity measurements end point. The EC50 values (146-1670 mg kg(-1)) calculated from the square root-X linear regression model differed significantly in various soils, although it was difficult to establish a causative relationship between soil physicochemical characteristic and phenanthrene toxicity. A significant factor in the assessment of soils vulnerability to the effect of phenanthrene was level of soil contamination, particularly with PAHs. Soils with previous contamination were more susceptible (mean EC50, 325 mg kg(-1)) than soils from uncontaminated, rural areas (mean EC50, 603 mg kg(-1)).     

Mercury speciation in highly contaminated soils from chlor-alkali plants using chemical extractions

A four-step novel sequential extraction procedure (SEP) was developed to assess Hg fractionation and mobility in three highly contaminated soils from chlor-alkali plants (CAPs). The SEP was validated using a certified reference material (CRM) and pure Hg compounds. Total, volatile, and methyl Hg concentrations were also determined using single extractions. Mercury was separated into four fractions defined as water-soluble (F1), exchangeable (F2) (0.5 M NH4Ac-EDTA and 1 M CaCl2 were tested), organic (F3) (successive extractions with 0.2 M NaOH and CH3COOH 4% [v/v]), and residual (F4) (HNO3 + H2SO4 + HClO4). The soil characterization revealed extremely contaminated (295 +/- 18 to 11 500 +/- 500 mg Hg kg(-1)) coarse-grained sandy soils having an alkaline pH (7.9-9.1), high chloride concentrations (5-35 mg kg(-1)), and very low organic carbon content (0.00-18.2 g kg(-1)). Methyl Hg concentrations were low (0.2-19.3 microg kg(-1)) in all soils. Sequential extractions indicated that the majority of the Hg was associated with the residual fraction (F4). In Soils 1 and 3, however, high percentages (88-98%) of the total Hg were present as volatile Hg. Therefore, in these two soils, a high proportion of volatile Hg was present in the residual fraction. The nonresidual fraction (F1 + F2 + F3) was most abundant in Soil 1 (14-42%), suggesting a higher availability of Hg in this soil. The developed and validated SEP was reproducible and efficient for highly contaminated samples. Recovery ranged between 93 and 98% for the CRM and 70 and 130% for the CAP-contaminated soils.     

Assessment of contamination from arsenical pesticide use on orchards in the Great Valley region, Virginia and West Virginia, USA

Lead arsenate pesticides were widely used in apple orchards from 1925 to 1955. Soils from historic orchards in four counties in Virginia and West Virginia contained elevated concentrations of As and Pb, consistent with an arsenical pesticide source. Arsenic concentrations in approximately 50% of the orchard site soils and approximately 1% of reference site soils exceed the USEPA Preliminary Remediation Goal (PRG) screening guideline of 22 mg kg(-1) for As in residential soil, defined on the basis of combined chronic exposure risk. Approximately 5% of orchard site soils exceed the USEPA PRG for Pb of 400 mg kg(-1) in residential soil; no reference site soils sampled exceed this value. A variety of statistical methods were used to characterize the occurrence, distribution, and dispersion of arsenical pesticide residues in soils, stream sediments, and ground waters relative to landscape features and likely background conditions. Concentrations of Zn, Pb, and Cu were most strongly associated with high developed land density and population density, whereas elevated concentrations of As were weakly correlated with high orchard density, consistent with a pesticide residue source. Arsenic concentrations in ground water wells in the region are generally <0.005 mg L(-1). There was no spatial association between As concentrations in ground water and proximity to orchards. Arsenic had limited mobility into ground water from surface soils contaminated with arsenical pesticide residues at concentrations typically found in orchards.     

Biosolids effects on phosphorus retention and release in some sandy Florida soils

The soil solid phase components most responsible for P sorption in Florida soils are Fe and Al oxides. Thus, we hypothesized that land application of biosolids would significantly increase a soil's P retention by increasing its content of P-sorbing solids, especially when biosolids with high Fe and Al concentrations are applied to soils that sorb P poorly. Biosolids effects were quantified by a series of single-point isotherms on soils from two field studies sampled for up to 4 yr after initial biosolids application. Biosolids additions had little effect on P retention in a soil with abundant oxalate-extractable Fe and Al and a correspondingly large native P-sorbing capacity. However, biosolids significantly increased P retention in a soil with low oxalate-extractable Fe and Al content and low native P-sorbing capacity. Biosolids effects on P retention lasted 1 to 3 yr after application, depending on biosolids source and rate of application, and generally mimicked persistence of increased extractable Fe and Al concentrations in the poorly P-sorbing soil. Disappearance of added Fe and Al (and, hence, P retention capacity) from the surface horizons over time was relatively rapid, perhaps due to abundant organic acid production associated with biosolids degradation. Phosphorus in biosolids containing (or tailored to contain) abundant Fe and/or Al can be expected to behave as a slowly available P source, and to be less subject to leaching losses than completely soluble P sources.     

Soil-to-root transfer and translocation of polycyclic aromatic hydrocarbons by vegetables grown on industrial contaminated soils

Polycyclic aromatic hydrocarbons (PAHs) are possible contaminants in some former industrial sites, representing a potential risk to human health if these sites are converted to residential areas. This work was conducted to determine whether PAHs present in contaminated soils are transferred to edible parts of selected vegetables. Soils were sampled from a former gasworks and a private garden, exhibiting a range of PAH concentrations (4 to 53 to 172 to 1263 and 2526 mg PAHs kg-1 of dry soil), and pot experiments were conducted in a greenhouse with lettuce (Lactuca sativa L. var. Reine de Mai), potato (Solanum tuberosum L. var. Belle de Fontenay), and carrot (Daucus carota L. var. Nantaise). At harvest, above- and below ground biomass were determined and the PAH concentrations in soil were measured. In parallel, plates were placed in the greenhouse to estimate the average PAH-dust deposition. Results showed that the presence of PAHs in soils had no detrimental effect on plant growth. Polycyclic aromatic hydrocarbons were detected in all plants grown in contaminated soils. However, their concentration was low compared with the initial soil concentration, and the bioconcentration factors were low (i.e., ranging from 13.4 x 10(-4) in potato and carrot pulp to 2 x 10(-2) in potato and carrot leaves). Except in peeled potatoes, the PAH concentration in vegetables increased with the PAH concentration in soils. The PAH distribution profiles in plant tissues and in soils suggested that root uptake was the main pathway for high molecular weight PAHs. On the opposite, lower molecular weight PAHs were probably taken up from the atmosphere through the leaves as well as by roots.     

Soil sulfur amendments suppress selenium uptake by alfalfa and Western wheatgrass

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

Behavior of 14C-atrazine in Argentinean topsoils under different cropping managements

Atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) behavior was studied in four surface soils during incubations in laboratory conditions. Soils were chosen in relation to their cropping management (tillage and no tillage) and crop rotation system (continuous soybean [Glycine mar (L.) Merr.] and maize (Zea mays L.)-soybean rotation). A natural soil under brushwood was sampled as a reference. Atrazine use in field conditions was associated with maize cropping, thus only one soil received atrazine every other year. Atrazine behavior was characterized through the balance of 14C-U-ring atrazine radioactivity among the mineralized fraction, the extractable fraction, and the nonextractable bound residues. Soil organic matter capacity to form bound residues was characterized using soil size fractionation. Accelerated atrazine mineralization was only observed in the soil receiving atrazine in field conditions. Atrazine application every other year was enough to develop a microflora adapted to triazine ring mineralization. Bound residue formation was rapid and increased with soil organic matter content. The coarsest soil size fractions (2000-200 and 200-50 microm) containing the nonhumified organic matter presented the highest capacity to form bound residues. No effect of tillage system was observed, probably because of the uniform sampling depth at 20 cm, hiding the stratification pattern of soil organic matter in non-tilled soils.     

Mechanisms of nutrient attenuation in a subsurface flow riparian wetland

Riparian wetlands are transition zones between terrestrial and aquatic environments that have the potential to serve as nutrient filters for surface and ground water due to their topographic location. We investigated a riparian wetland that had been receiving intermittent inputs of NO3- and PO4(3-) during storm runoff events to determine the mechanisms of nutrient attenuation in the wetland soils. Few studies have shown whether infrequent pulses of NO3- are sufficient to maintain substantial denitrifying communities. Denitrification rates were highest at the upstream side of the wetland where nutrient-rich runoff first enters the wetland (17-58 microg N2O-N kg soil(-1) h(-1)) and decreased further into the wetland. Carbon limitation for denitrification was minor in the wetland soils. Samples not amended with dextrose had 75% of the denitrification rate of samples with excess dextrose C. Phosphate sorption isotherms suggested that the wetland soils had a high capacity for P retention. The calculated soil PO4(3-) concentration that would yield an equilibrium aqueous P04(3-) concentration of 0.05 mg P L(-1) was found to be 100 times greater than the soil PO4(3-) concentration at the time of sampling. This indicated that the wetland could retain a large additional mass of PO4(3-) without increasing the dissolved P04(3-) concentrations above USEPA recommended levels for lentic waters. These results demonstrated that denitrification can be substantial in systems receiving pulsed NO3- inputs and that sorption could account for extensive PO4(3-) attenuation observed at this site.     

Fate of pesticides in tropical soils of Brazil under field conditions

The potential of pesticides for nonpoint ground water pollution depends on their dissipation and leaching behavior in soils. We investigated the fate of 10 pesticides in two tropical soils of contrasting texture in the Brazilian Cerrado region near Cuiabá during an 80-d period, employing topsoil dissipation studies, soil core analyses, and lysimeter experiments. Dissipation of pesticides was rapid, with field half-lives ranging from 0.8 to 20 d in Ustox and 0.6 to 11.8 d in Psamments soils. Soil core analyses showed progressive leaching of polar pesticides in Psamments, whereas in Ustox pesticides were rapidly transported to 40 cm soil depth regardless of their sorption properties, suggesting that leaching was caused by preferential flow. In lysimeter experiments (35 cm soil depth), cumulative leaching was generally low, with < or = 0.02% and < or = 0.19% of the applied amounts leached in Ustox and Psamments, respectively. In both soils, all pesticides but the pyrethroids were detected in percolate at 35 cm soil depth within the first 6 d after application. Cumulative efflux and mean concentrations of pesticides in percolate were dosely correlated with their Groundwater Ubiquity Score (GUS). The presence of alachlor (2-chloro-2', 6'-diethyl-N-methoxymethylacetanilide), atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine), metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide], simazine [2-chloro-4,6-bis(ethylamino)-1,3,5-triazine], and trifluralin (2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline) throughout the soil profile and in percolate of wick lysimeters at 95 cm soil depth indicated that a nonpoint pollution of ground water resources in tropical Brazil cannot be ruled out for these substances.     

Sorption kinetics and equilibria of organic pesticides in carbonatic soils from South Florida

A batch reactor was used to determine sorption kinetic parameters (k2, F, and K*) and the equilibrium sorption coefficient (K). The two-site nonequilibrium (TSNE) batch sorption kinetics model was used to calculate the kinetic parameters. Two probe organic pesticides, atrazine [2-chloro-4-ethylamino-6-isopropylamino-s-triazine] and diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] were studied using three carbonatic soils from South Florida (Chekika, Perrine, and Krome), one noncarbonatic soil from Iowa (Webster), and one organic soil (Lauderhill) from South Florida. Carbonatic soils contained more than 600 g kg(-1) CaCO3. Sorption is initially very fast up to 3 h and then slowly reaches equilibrium. All soil-chemical combinations reached sorption equilibrium after about 24 h and all sorption isotherms were linear. The sorption kinetics data were well described by the TSNE model for all soil-chemical combinations except for the marl soil data (Perrine-Atrazine), which were better described by the one-site nonequilibrium (OSNE) model. Diuron, with higher K, undergoes slower sorption kinetics than atrazine. The Lauderhill soil containing organic carbon (OC) of 450 g kg(-1) exhibited slowest sorption kinetics for both pesticides. An inverse relationship between k3 and K was observed for atrazine and diuron separately in Chekika, Webster, and Lauderhill soils but not in Perrine and Krome soils. The sorption kinetic parameters were used to distinguish the sorption behavior between atrazine and diuron and to identify differences between soils. Normalizing the sorption coefficient (K) to OC showed that atrazine and diuron had K oc values in carbonatic soils that were a third of reported literature values for noncarbonatic soils. Using existing literature K oc values in solute transport models will most likely underestimate the mobility of atrazine, diuron, and other neutral organic chemicals in carbonatic soils.     

Retention and runoff losses of atrazine and metribuzin in soil

Minimizing herbicide runoff and mobility in the soil and thus potential contamination of water resources is a national concern. Metribuzin [4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5(4H)-one] and atrazine [2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine] dynamics in surface soils and in runoff waters were studied on six 0.2-ha sugarcane (Saccharum spp.) plots of a Commerce silt loam (fine-silty, mixed, superactive, nonacid, thermic Fluvaquentic Endoaquept) during three growing seasons under different best management practices. Metribuzin was applied in the spring as a postemergence herbicide and atrazine was applied following winter harvest. Both herbicides were applied on top of the sugarcane rows as 0.6- or 0.9-m band width application, or broadcast application, where the entire area was treated. Maximum effluent concentrations were measured from the broadcast treatment and ranged from 600 to 1100 microg L(-1) for atrazine and 250 to 450 microg L(-1) for metribuzin. Atrazine runoff losses were highest for the broadcast treatment (2.8-11% of that applied) and lowest for the 0.6-m band treatment (1.9-7.6%), with a similar trend for metribuzin losses. Measured extractable herbicides from the surface soil exhibited a sharp decrease with time and were well described with a simple first-order decay model. For atrazine, estimates for the decay rate (lambda) were higher than for metribuzin. Results based on laboratory adsorption-desorption (kinetic-batch) measurements were consistent with field observations. The distribution coefficients (Kd) for atrazine exhibited stronger retention over time in comparison with metribuzin on the Commerce soil. Moreover, discrepancies between adsorption isotherm and desorption indicated slower release and that hysteresis was more pronounced for atrazine compared with metribuzin.     

Phosphorus and nitrogen sorption to soils in the presence of poultry litter-derived dissolved organic matter

Two environmental aspects associated with land application of poultry litter that have not been comprehensively evaluated are (i) the competition of dissolved organic matter (DOM) and P for soil sorption sites, and (ii) the sorption of dissolved organic nitrogen (DON) relative to inorganic nitrogen species (e.g., NO(3)(-) and NH(4)(+)) and dissolved organic carbon (DOC). The competition between DOM and P for sorption sites has often been assumed to increase the amount of P available for plant growth; however, elevating DOM concentrations may also increase P available for transport to water resources. Batch sorption experiments were conducted to (i) evaluate soil properties governing P sorption to benchmark soils of Southwestern Missouri, (ii) elucidate the impact of poultry litter-derived DOM on P sorption, and (iii) investigate DON retention relative to inorganic N species and DOC. Soils were reacted for 24 h with inorganic P (0-60 mg L(-1)) in the presence and absence of DOM (145 mg C L(-1)) using a background electrolyte solution comparable to DOM extracts (I = 10.8 mmol L(-1); pH 7.7). Soil P sorption was positively correlated with metal oxide (r(2) = 0.70) and clay content (r(2) = 0.79) and negatively correlated with Bray-1 extractable P (r(2) = 0.79). Poultry litter-derived DOM had no significant negative impact on P sorption. Dissolved organic nitrogen was preferentially removed from solution relative to (NO(3)(-)-N + NO(2)(-)-N), NH(4)(+)-N, and DOC. This research indicates that poultry litter-derived DOM is not likely to enhance inorganic P transport which contradicts the assumption that DOM released from organic wastes increases plant-available P when organic amendments and fertilizer P are co-applied. Additionally, this work demonstrates the need to further evaluate the fate and transport of DON in agroecosystem soils receiving poultry litter applications.     

Phosphorus sorption and availability in soils amended with animal manures and sewage sludge

Soils that receive large applications of animal wastes and sewage sludge are vulnerable to releasing environmentally significant concentrations of dissolved P available to subsurface flow owing to the gradual saturation of the soil's P sorption capacity. This study evaluated P sorption (calculated from Langmuir isotherms) and availability of P (as CaCl2-P and resin P) in soils incubated for 20 d with poultry litter, poultry manure, cattle slurry, municipal sewage sludge, or KH2PO4, added on a P-equivalent basis (100 mg P kg(-1)). All the P sources had a marked negative effect on P sorption and a positive effect on P availability in all soils. In the cattle slurry- and KH2PO4-treated soils, the decreases in P sorption maximum (19-66%) and binding energy (25-89%) were consistently larger than the corresponding decreases (7-41% and 11-30%) in poultry litter-, poultry manure-, and sewage sludge-treated soils. The effects of cattle slurry and KH2PO4 on P availability were, in most cases, larger than those of the other P sources. In the poultry litter, poultry manure, and sewage sludge treatments, the increase in soil solution P was inversely related (R2 = 0.75) to the input of Ca from these relatively high Ca (13.5-42 g kg(-1)) sources. Correlation analyses implied that the magnitude of the changes in P sorption and availability was not related to the water-extractable P content of the P sources. Future research on the sustainable application of organic wastes to agricultural soils needs to consider the non-P- as well as P-containing components of the waste.     

Regionalizing potential for microbial bypass flow through New Zealand soils

Microbial breakthrough curves of 12 soils, generated by the application of dairy shed effluent followed by continuous artificial rainfall for one pore volume at 5 mm h(-1) onto large undisturbed soil cores, have been ranked as high, medium, or low potential for microbial bypass flow. The ranking is based on the position of the peak in the breakthrough curve. Knowledge of soil properties that affect microbial transport through soil gained from the microbial breakthrough curves was linked to soil classes, or to their accessory properties, of the New Zealand Soil Classification. Spatial depiction of the ratings has been achieved via the national 1:50,000 scale soil map. Soils with a drainage impediment or those with well developed soil structure have a high potential for microbial bypass flow, whereas soils from tephra and Recent Soils with less developed, porous, soil structure have a low potential for microbial bypass flow. The risk rankings should be considered as maxima because management may change some rankings.     

Soil water nitrate and ammonium dynamics under a sewage effluent irrigated eucalypt plantation

Managed forests and plantations are appropriate ecosystems for land-based treatment of effluent, but concerns remain regarding nutrient contamination of ground- and surface waters. Monthly NO3-N and NH4-N concentrations in soil water, accumulated soil N, and gross ammonification and nitrification rates were measured in the second year of a second rotation of an effluent irrigated Eucalyptus globulus plantation in southern Western Australia to investigate the separate and interactive effects of drip and sprinkler irrigation, effluent and water irrigation, irrigation rate, and harvest residues retention. Nitrate concentrations of soil water were greater under effluent irrigation than water irrigation but remained <15 mg L(-1) when irrigated at the normal rate (1.5-2.0 mm d(-1)), and there was little evidence of downward movement. In contrast, NH4-N concentrations of soil water at 30 and 100 cm were generally greater under effluent irrigation than water irrigation when irrigated at the normal rate because of direct effluent NH4-N input and indirect ammonification of soil organic N. Drip irrigation of effluent approximately doubled peak NO3-N and NH4-N concentrations in soil water. Harvest residue retention reduced concentrations of soil water NO3-N at 30 cm during active sprinkler irrigation, but after 1 yr of irrigation there was no significant difference in the amount of N stored in the soil system, although harvest residue retention did enhance the "nitrate flush" in the following spring. Gross mineralization rates without irrigation increased with harvest residue retention and further increased with water irrigation. Irrigation with effluent further increased gross nitrification to 3.1 mg N kg(-1) d(-1) when harvest residues were retained but had no effect on gross ammonification, which suggested the importance of heterotrophic nitrification. The downward movement of N under effluent irrigation was dominated by NH4-N rather than NO3-N. Improving the capacity of forest soils to store and transform N inputs through organic matter management must consider the dynamic equilibrium between N input, uptake, and immobilization according to soil C status, and the effect changing microbial processes and environmental conditions can have on this equilibrium.     

Properties of several fly ash materials in relation to use as soil amendments

Fly ash samples from five power stations in Western Australia and Queensland, and two soils used for horticulture in Western Australia, were evaluated for a series of physical and chemical properties. Soils were comprised primarily of coarse sand-sized particles, whereas most of the fly ashes were primarily fine sand- and silt-sized particles. Hydraulic conductivities in the fly ashes were 105- to 248-fold slower than in the soils. The water-holding capacities of fly ashes at "field capacity" were three times higher than those of the soils. Extractable P in the fly ashes (except Tarong and Callide) were 20- to 88-fold higher than in the soils. The pH showed considerable variation among the different sources of fly ash, with samples from Muja being the most acidic (pH = 3.8; 1:5 in CaCl2 extract) and from Gladstone the most alkaline (pH = 9.9). The toxicity characteristic leaching procedure (TCLP) values indicate that the potential for release of trace elements from the fly ashes was well below regulatory levels. When applied at sufficient rates (e.g., to achieve 10% w/w in surface layers) to sandy soils, fly ash altered texture and increased water-holding capacity. Depending on the source of fly ash used, such amendments could also provide P and aid nutrient retention by increasing the phosphorus retention index (PRI) and/or cation exchange capacity (CEC). The considerable variability in physical and chemical properties among the fly ash samples evaluated in the present study supports the notion that field trials are essential to the future development of soil amendment strategies making use of any particular source of fly ash.