Size distribution of organic matter and associated propiconazole in agricultural runoff material

Sorption and desorption characteristics of propiconazole (1-[[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole) to different particle/aggregate-size fractions of agricultural runoff material were investigated. Emphasis was put on clay and colloidal size fractions to evaluate their role as potential sorbents and carriers for this pesticide. The runoff material was separated into size fractions ranging from 2 mm to ca. 15 nm by wet sieving, sedimentation, centrifugation, and membrane ultrafiltration. Each fraction was characterized by its organic C content and C/N ratio. Distinctive sorption properties of clay-sized particles and colloids were investigated. The obtained size fractions differed significantly in their organic C concentration, C/N ratio, and sorption properties to propiconazole. Organic matter was mainly associated in aggregates >2 microm. Binding of propiconazole to this coarse fraction made up 80% of the sorbed propiconazole. The distribution coefficient between solid and aqueous phases increased with decreasing particle size. The colloidal fraction (<0.16 microm) exhibited the highest sorbtivity, with a distribution coefficient of 113 L kg(-1), which was more than four times higher than that in the bulk sample (27 L kg(-1)). The fraction <2 microm represented 8% of the total sample weight, but contributed to 20% of the sorbed propiconazole. Strong hysteresis was observed for the sorption-desorption of propiconazole on the runoff material. Under dilution very little sorbed propiconazole will be released into the water phase. Due to its high sorbtivity and mobility and the strong sorption-desorption hysteresis, particles in the fraction <2 microm can be important carriers of propiconazole in runoff suspensions with high sediment load.     

Use of Constructed Wetlands for Urban Stream Restoration: A Critical Analysis

/ Investigation of a delta marsh restoration project proposed forthe Don River in Toronto, Ontario, underlines several concerns aboutconstructed wetland projects designed for water quality improvement andaquatic habitat enhancement. The Don is a highly urbanized river that hasundergone significant physiographic modifications and continually receives acomplex mixture of conventional, metallic, and organic contaminants frommultiple point and nonpoint sources. Rather than providing permanent removalof urban contaminants, wetland processes offer a limited capacity fortemporary storage of contaminant inputs, and potential reactions may actuallyproduce more toxic and/or bioavailable forms of some chemicals. Theseprocesses tend to result in the concentration of watershed contaminants inwetland vegetation and sediments. As the restored marsh would be availablefor spawning and feeding by aquatic fauna, the potential exists for chemicalbioconcentration and biomagnification through the aquatic community.Accordingly, wetland systems are not suited to the dual purposes of waterquality improvement and aquatic habitat enhancement. Upstream controls,including source reduction of contaminant inputs, are recommended asessential components of all constructed wetland projects.KEY WORDS: Constructed wetlands; Water quality; Ecological restoration;Don River     

Effects of mineral surfaces on pyrene partitioning to well-characterized humic substances

Mineral surfaces can alter the ability of humic substances (HS) to bind hydrophobic organic contaminants. In this study, complete adsorption (i.e., to avoid HS adsorptive fractionation effects) of a small subset of well-characterized terrestrial and aquatic HS on kaolinite and hematite significantly changed their subsequent organic carbon-normalized partition coefficients K(ads)(oc) for pyrene relative to their original respective dissolved organic carbon-normalized partition coefficients K(dis)(oc). Parallel experiments with ultrafiltration (UF) fractions obtained from purified Aldrich humic acid (PAHA) (Aldrich Chemical, Milwaukee, WI) gave similar results. The heterogeneity among the PAHA UF fractions was examined via their mineral surface adsorption characteristics and their subsequent ability to bind pyrene. As expected, variations in maximum adsorption densities (q(max)), Langmuir adsorption constants (K(q)), and pyrene K(ads)(oc) values were observed among the PAHA UF fractions. However, general trends of q(max), K(q), and pyrene log K(ads)(oc) values for the PAHA UF fractions versus the logarithm of their weight-average molecular weights (MW(w)) did not typically match the corresponding trends obtained with the four aquatic and terrestrial HS. In general, an ideal mixture competitive adsorption model gave reasonable predictions for PAHA sorption to kaolinite and hematite based on their corresponding UF isotherm parameters. Ideal mixture predictions of pyrene partitioning to adsorbed PAHA from the corresponding UF fraction results were better for kaolinite versus hematite, indicating that the underlying mineral surface can alter the effects of HS heterogeneity on hydrophobic organic contaminant sorption.     

Evaluating colloidal phosphorus delivery to surface waters from diffuse agricultural sources

Colloid-facilitated phosphorus (P) delivery from agricultural soils in different hydrological pathways was investigated using a series of laboratory and field experiments. A soil colloidal P test was developed that yields information on the propensity of different soils to release P attached to soil colloids. The relationship between turbidity of soil extracts and total phosphorus (TP) was significant (r2 = 0.996, p < 0.001) across a range of agricultural soils, and a strong positive relationship (r2 = 0.86, p < 0.001) was found between "colloidal P" (H2O-CaCl2 extracts) and turbidity. Linear regression of the proportion of fine clay (<2 microm) for each soil type evaluated against the (H2O-CaCl2) colloidal P fraction gave a weak but positive relationship (r2 = 0.38, p = 0.082). The relative contribution of different particle-size fractions in transporting P in agricultural runoff from grassland soils was evaluated using a randomized plot experiment. A significant difference (p = 0.05) in both TP and reactive phosphorus (RP) in subsurface flow was recorded for different particle-size fractions, with most TP transferred either in association with the 2-microm fraction or with the 0.001-microm or smaller fractions. Total P concentrations in runoff were higher from plots receiving P amendments compared with the zero-P plots; however, these differences were only significant for the >0.45-microm particle-size fractions (p = 0.05), and may be evidence of surface applications of organic and inorganic fertilizers being transferred through the soil either as intact organic colloids or attached to mineral particles. Our results highlight the potential for drainage water to mobilize colloids and associated P during rainfall events.     

Restoration and protection of aqueous environments by utilizing aquatic organisms

Summary Past and current uncontrolled dumping, land application and accidental spills of recalcitrant, toxic environmental pollutants such as DDT and polychlorinated biphenyls (PCBs) pose a continued world-wide environmental threat, in particular to aquatic environments. Bioaccumulative contaminants are rapidly absorbed out of water-borne ambient environments and concentrated in the tissues of living aquatic organisms at concentrations that can range from thousands to millions of times greater than levels in the ambient environment. These absorbed levels are high enough to cause dysfunction in the organisms and potential harmful effects to humans. An established technology capable of remediating the low contaminant levels originating in the ambient aquatic environment does not currently exist. This paper proposes the macro-bioremediation process whereby certain fish and other macroscopic aquatic organisms could be used to filter, concentrate and remove bioaccumulative contaminants from polluted aqueous systems. Contaminant removal would involve the harvesting and subsequent restocking of aquatic organisms capable of bioaccumulating high contaminant levels in relatively short time periods. Tissues of harvested organisms could be composted with specialized fungus and bacteria to fully degrade the recalcitrant contaminants. The macro-bioremediation process could be used at numerous geographic locations for the restoration of natural aquatic environments, supplemental wetlands treatment and for waste-water, hazardous waste and sludge treatment augmentation.     

Potential adverse effects of applying phosphate amendments to immobilize soil contaminants

Seven-day batch equilibrium experiments were conducted to measure the efficacy of four phosphate amendments (trisodium trimetaphosphate [TP3], dodecasodium phytate [Na-IP6], precipitated calcium phytate [Ca-IP6], and hydroxyapatite [HA]) for immobilizing Ni and U in organic-rich sediment. Using the eight-step modified Miller's sequential extraction procedure and the USEPA's Toxicity Characteristic Leaching Procedure, the effect of these amendments on the distribution of Ni and U was assessed. Relative to unamended controls, equilibrium aqueous-phase U concentrations were lower following HA and Ca-IP6 additions but higher following TP3 and Na-IP6 amendments, whereas aqueous Ni concentrations were not decreased only in the Na-IP6 amended treatment relative to the control. The poor rates of contaminant immobilization following TP3 and Na-IP6 amendments correlate with the dispersion of organic matter and organo-mineral colloids, which probably contain sorbed U and Ni. While all amendments shifted the U distribution toward more recalcitrant soil fractions, Ni was redistributed to more labile soil fractions. This study cautions that the addition of orthophosphates and organophosphates as contaminant immobilizing amendments may in fact have adverse effects, especially in high-organic soils. Particular attention is warranted at sites with mixed contaminants with varying geochemical behaviors.     

Measuring runoff-suspended solids using an improved turbidometer method

Differences in particle size distribution between runoff standards and unknown samples affect the accuracy of estimation of total suspended solids (TSS) concentration using the nephelometric turbidity (NTU) method. The objective was to quantify the effects of a sucrose solution as suspending medium and contrasting particle size distribution on nephelometric turbidity and accuracy of TSS estimation. Nineteen benchmark soils varying in texture and color were divided into particle size distribution of <250 and <2000 microm. Soils from these two aggregate classes were then made into suspension ranging from 0.2 to 15 g L-1 using distilled deionized water. Runoff suspensions ranging from 0.2 to 21 g L-1 were also collected from different watersheds. Turbidity of soil and runoff suspensions was measured in sucrose solution and in distilled deionized water. The sucrose solution density ranged from 1.10 to 1.30 kg L-1. Increasing sucrose solution density decreased turbidity. The TSS concentration was most sensitive to changes in turbidity with the 1.30 kg L-1 sucrose solution. Using the 1.30 kg L-1 sucrose solution, particle size bias and error of TSS estimates were decreased by at least 20% compared to distilled deionized water. Reduction in refraction index differences between the suspended particles and sucrose solution combined with reduced particle settling and reduced Brownian motion resulted in dampening the effects of particle size distribution. We propose a sucrose solution of 1.30 kg L-1 as a better suspending medium to dampen the effect of particle size distribution and thus improve suspension TSS concentration estimation.     

Immobilization of nickel and other metals in contaminated sediments by hydroxyapatite addition

Batch experiments were conducted to evaluate the ability of hydroxyapatte (HA) to reduce the solubility of metals, including the primary contaminants of concern, Ni and U, from contaminated sediments located on the Department of Energy's Savannah River Site, near Aiken, SC. Hydroxyapatitie was added to the sediments at application rates of 0, 5, 15.8, and 50 g kg-1. After equilibrating in either 0.02 M KCl or 0.01 M CaCl2, the samples were centrifuged and the supernatants filtered prior to metal, dissolved organic C, and PO4 analyses. The treated soils were then air-dried and changes in solid-phase metal distribution were evaluated using sequential extractions and electron-based microanalysis techniques. Hydroxyapatite was effective at reducing the solubility of U and, to a lesser degree, Ni. Hydroxyapatite was also effective in reducing the solubility of Al, Ba, Cd, Co, Mn, and Pb. Sequential extractions indicate that HA transfers such metals from more chemically labile forms, such as the water-soluble and exchangeable fractions, by altering solid-phase speciation in favor of secondary phosphate precipitates. Hydroxyapatite effectiveness was somewhat reduced in the presence of soluble organics that likely increased contaminant metal solubility through complexation. Arsenic and Cr solubility increased with HA addition, suggesting that the increase in pH and competition from PO4 reduced sorption of oxyanion contaminants. Energy dispersive x-ray (EDXA) analysis conducted in the transmission electron microscope (TEM) confirmed that HA amendment sequesters U, Ni, Pb, and possibly other contaminant metals in association with secondary Al-phosphates.     

Stabilization of composted organic matter after application to a humus-free sandy mining soil

The use of mining substrates for recultivation purposes is limited due to their low organic matter (OM) contents. In a 1-yr laboratory experiment we evaluated the stabilization of biowaste compost added to a humus-free sandy mining soil to examine the suitability of compost amendment for the formation of stable soil organic matter (SOM). The stabilization process was characterized by measuring enrichment of OM and nitrogen in particle size fractions obtained after dispersion with different amounts of energy (ultrasonication and shaking in water), carbon mineralization, and amount of dissolved organic carbon (DOC). During the experiment, 17.1% of the organic carbon (OC) was mineralized. Organic carbon enrichment in the < 20-micron particle size fraction at the beginning of the experiment was in the range of natural soils with similar texture. Within 12 mo, a distinct OC redistribution from coarse into fine fractions was found with both dispersion methods. The accumulation of OC was more pronounced for the size separates obtained by ultrasonication, where the carbon distribution between 0.45- to 20-micron particle size fractions increased from 30% at the beginning to 71% at the end of the experiment. Dissolved organic carbon contents ranged between 50 and 68 g kg-1 OC and decreased during the incubation. In conclusion, the exponential decrease of carbon mineralization and the OC enrichment in the fine particle size fractions both indicated a distinct OM stabilization in the mining soil.     

Packaging glass contained in the heavy residual fraction refused by Portuguese Mechanical and Biological Treatment plants

Mechanical and Biological Treatment (MBT) is an important strategy to manage Municipal Solid Waste (MSW) in Europe. The presence of recyclable materials on MSW depends on different factors such as inefficiencies in the Municipal Solid Waste collecting schemes and to the low level of citizenship environmental education. Among other products, MBT plants produce a residual fraction, named here as heavy residual fraction, that contains a significant amount of packaging glass which in Portugal is currently landfilled. This material is not recycled because it is heavily contaminated with other materials, preventing its processing in Material Recovery Facilities (MRF).In this paper the characterization, including particle size and composition, of the residual fraction of six Portuguese MBT plants is presented. The relevant variables that determine the heavy residual fraction characteristics were identified. It was observed that the MBTr particle size distribution is different and depends mainly on the place on the flowsheet where the MBTr exits the process, which is determined by the type of biological process and by the aperture of the last screen where the product passes through. The content in glass varies from 33 to 83%. These values are mainly related with the upstream glass sorting and with the efficiency of the recovery of the organic fraction which is the glass main contaminant. The second main contaminant is “stones”.The quantity of glass contained in this product in all the plants that will be in operation in Portugal in 2014 was estimated. The work shows that if all the 48,000 of glass could be recovered the Portuguese recycling rate would increase by 4.4%.     

Sorption of sulfonamide pharmaceutical antibiotics on whole soils and particle-size fractions

Residues of pharmaceutical antibiotics are found in the environment, whose fate and effects are governed by sorption. Thus, the extent and mechanisms of the soil sorption of p-aminobenzoic acid and five sulfonamide antibiotics (sulfanilamide, sulfadimidine, sulfadiazine, sulfadimethoxine, and sulfapyridine) were investigated using topsoils of fertilized and unfertilized Chernozem and their organic-mineral particle-size fractions. Freundlich adsorption coefficients (K(f)) ranged from 0.5 to 6.5. Adsorption increased with aromaticity and electronegativity of functional groups attached to the sulfonyl-phenylamine core. Adsorption to soil and particle-size fractions increased in the sequence: coarse silt < whole soil < medium silt < sand < clay < fine silt and was influenced by pH. Sorption nonlinearity (1/n 相似文献   

BIOLOGICAL INDICATORS AND BIOLOGICAL EFFECTS OF ESTUARINE/COASTAL POLLUTION1

ABSTRACT: Sustained interest in and concern about the health status of the aquatic environment has resulted in extensive research focused on (1) effects of pollution on survival, growth, and reproduction of resource species at all life stages; (2) diseases of fish and shellfish, as they may be related to pollution and as they may serve as indicators of environmental stress; and (3) contaminant body burdens in fish and shellfish - their effects on the aquatic animals and their potential effects on humans. Effects, lethal and sublethal, of pollutants on life history stages of fish and shellfish have been documented, as have impacts on local stocks in badly degraded habitats, but as yet there has been no adequate quantitative demonstration of effects on entire aquatic species - probably because of the difficulty in sorting out relative effects of the many environmental factors that influence abundance. Sublethal effects, especially those that result in disease, have been examined intensively, and some diseases and disease syndromes have been associated statistically with pollution. Other pollution indicators (biochemical, physiological, genetic, behavioral, and ecological) have also received some attention, as have body burdens of contaminants in aquatic species. Research, especially that conducted during the past decade, has done much to clarify the many pathways and toxic effects of contaminants on aquatic animals, and has also helped to identify mechanisms for survival of fish and shellfish in the presence of environmental changes caused by human activities.     

Investigations of Contaminated Fluvial Sediment Deposits: Merging of Statistical and Geomorphic Approaches

Concentrations of contaminants in sediment deposits can have large spatial variability resulting from geomorphic processes acting over long time periods. Thus, systematic (e.g., regularly spaced sample locations) or random sampling approaches might be inefficient and/or lead to highly biased results. We demonstrate the bias associated with systematic sampling and compare these results to those achieved by methods that merge a geomorphic approach to evaluating the physical system and stratified random sampling concepts. By combining these approaches, we achieve a more efficient and less biased characterization of sediment contamination in fluvial systems. These methods are applied using a phased sampling approach to characterize radiological contamination in sediment deposits in two semiarid canyons that have received historical releases from the Los Alamos National Laboratory. Uncertainty in contaminant inventory was used as a metric to evaluate the adequacy of sampling during these phased investigations. Simple, one-dimensional Monte Carlo simulations were used to estimate uncertainty in contaminant inventory. We also show how one can use stratified random sampling theory to help estimate uncertainty in mean contaminant concentrations.     

Wastewater reuse and predicted ecological risk posed by contaminant mixtures in Potomac River watershed streams

A wastewater model was applied to the Potomac River watershed to provide (i) a means to identify streams with a high likelihood of carrying elevated effluent-derived contaminants and (ii) risk assessments to aquatic life and drinking water. The model linked effluent discharges along stream networks, accumulated wastewater, and predicted contaminant loads of municipal wastewater constituents while accounting for instream dilution and attenuation. Simulations using 2016 data suggested that nearly 30% (8281 km) of streams were wastewater impacted. Low- to medium-order streams had the largest range of accumulated wastewater (ACCWW%) values. ACCWW% exceeded a 1% threshold at >39% of drinking-water intakes (varied by temporal condition). Risk assessments of municipal wastewater-contaminant mixtures indicated that 22% (1479 km) of streams impacted by municipal wastewater (5.5% of all reaches modeled) may pose high risk to aquatic organisms under mean-annual conditions, with fish more susceptible to chronic-exposure effects relative to other taxa. Risk varied temporally and by stream order, with the greatest risk occurring in the summer in small streams. These findings suggest that wastewater may be an important factor contributing to environmental degradation in the Potomac River watershed.     

Magnetic particle technology in environmental remediation and wildlife rehabilitation

The use of magnetic particles in environmental remediation and wildlife rehabilitation is currently under investigation at Victoria University, in collaboration with the Phillip Island Research Centre, Victoria, Australia. Iron powder has been shown to be very effective for the magnetic cleansing of feathers and plumage and is almost ideal for this purpose, being non-toxic, a non-irritant and recyclable. Detailed investigations have demonstrated that by varying particle size, particle structure and surface texture, the efficacy of oil removal from feathers and plumage can be successfully manipulated. In this regard, it is possible to identify a grade of iron powder whereby, within experimental error, effectively 100% removal of a variety of fresh contaminants from different matrices, including feathers, can be achieved. Our investigations have been extended to the application of such particles to the successful removal of tarry and weathered/tarry contamination. The results of these investigations have indicated that, for such contaminants, removals ranging from 97–99% may be achieved. Magnetic particle technology may also be adapted for the screening of pre-conditioning agents that can further assist in the removal of tarry and weathered/tarry contamination from feathers. These investigations suggest that magnetic particles could have an important role to play in environmental remediation and wildlife rehabilitation as a clean and effective technology.     

C and N Content in Density Fractions of Whole Soil and Soil Size Fraction Under Cacao Agroforestry Systems and Natural Forest in Bahia,Brazil

Agroforestry systems (AFSs) have an important role in capturing above and below ground soil carbon and play a dominant role in mitigation of atmospheric CO₂. Attempts has been made here to identify soil organic matter fractions in the cacao-AFSs that have different susceptibility to microbial decomposition and further represent the basis of understanding soil C dynamics. The objective of this study was to characterize the organic matter density fractions and soil size fractions in soils of two types of cacao agroforestry systems and to compare with an adjacent natural forest in Bahia, Brazil. The land-use systems studied were: (1) a 30-year-old stand of natural forest with cacao (cacao cabruca), (2) a 30-year-old stand of cacao with Erythrina glauca as shade trees (cacao + erythrina), and (3) an adjacent natural forest without cacao. Soil samples were collected from 0-10 cm depth layer in reddish-yellow Oxisols. Soil samples was separated by wet sieving into five fraction-size classes (>2000 μm, 1000–2000 μm, 250–1000 μm, 53–250 μm, and <53 μm). C and N accumulated in to the light (free- and intra-aggregate density fractions) and heavy fractions of whole soil and soil size fraction were determined. Soil size fraction obtained in cacao AFS soils consisted mainly (65 %) of mega-aggregates (>2000 μm) mixed with macroaggregates (32–34%), and microaggregates (1–1.3%). Soil organic carbon (SOC) and total N content increased with increasing soil size fraction in all land-use systems. Organic C-to-total N ratio was higher in the macroaggregate than in the microaggregate. In general, in natural forest and cacao cabruca the contribution of C and N in the light and heavy fractions was similar. However, in cacao + erythrina the heavy fraction was the most common and contributed 67% of C and 63% of N. Finding of this study shows that the majority of C and N in all three systems studied are found in macroaggregates, particularly in the 250–1000 μm size aggregate class. The heavy fraction was the most common organic matter fraction in these soils. Thus, in mature cacao AFS on highly weathered soils the main mechanisms of C stabilization could be the physical protection within macroaggregate structures thereby minimizing the impact of conversion of forest to cacao AFS.     

Size distributions of fine and ultrafine particles in the city of Strasbourg: correlation between number of particles and concentrations of NO(x) and SO(2) gases and some soluble ions concentration determination

An Electrical Low Pressure Impactor (ELPI) was used during spring and autumn 2003 in the centre of Strasbourg for the measurement of atmospheric aerosols size distribution. The concentration of NO(x) and SO(2) in air was simultaneously measured with specific analysers. Samples were collected in the range 0.007-10 microm in equivalent aerodynamic diameter size. Number distributions are representative of a pollution originating from urban traffic with a particle size distribution exhibiting a nucleation mode below 29 nm and an accumulation mode around 80 nm in size. A mean particle density equal to 39000+/-35000 total particles per cm(3) with a size ranging from 7 to 10 microm was obtained after a sampling period of 2 weeks in spring. About 86.9% of the number of particles have an aerodynamic diameter below 0.1 microm and 13.1% between 0.1 and 1 microm. Correlation coefficients between the number of particles impacted on each ELPI plate and gas concentrations (SO(2) and NO(x)) showed that the numbers of particles with diameter between 0.10 and 0.62 microm are highly related to the NO(x) concentration. This result indicates that particles are traffic induced since NO(x) is mainly emitted by cars as shown by measurements on various sites. Particles are less clearly correlated to the SO(2) concentration. Particle analysis on different ELPI plates for a sampling period of 2 weeks in autumn showed high level of soluble NO(3)(-), SO(4)(2-) and NH(4)(+) ions. Indeed, up to 90% b.w. of these three species were found in the particle range 0.1-1 microm. The formation of particulate NH(4)NO(3) is favoured by high NO(x) concentration, which induces the formation of gaseous HNO(3).     

Reductive dechlorination of activated carbon-adsorbed trichloroethylene by zero-valent iron: carbon as electron shuttle

Sequestration of organic contaminants in carbonaceous materials can significantly affect contaminant fate and transport. We investigated the reductive dechlorination of granular-activated carbon (GAC)-adsorbed trichloroethylene (TCE) by nanoscale zero-valent iron (nZVI) to understand the effect of sequestration on abiotic reactivity of organic contaminants. Significant reduction of TCE sequestered in GAC micropores was observed, even though direct contact with nZVI was unlikely. Reduction of sequestered TCE by reactive Fe(II) species or molecular hydrogen was ruled out as the reaction mechanisms. We propose that GAC served as the conductor for the transfer of electrons or atomic hydrogen from nZVI to the micropores, wherein adsorbed TCE molecules were reduced. An important implication for environmental remediation is that carbonaceous adsorbents not only function as a superb sink for organic contaminants but also allow them to be slowly degraded while being trapped.