Immobilization of cesium-137 and uranium in contaminated sediments using soil amendments

Batch and dynamic leaching methods were used to evaluate the effectiveness of hydroxyapatite (HA), illite, and zeolite, alone and in combination, as soil additives for reducing the migration of cesium-137 (137Cs+) and uranium (U) from contaminated sediments. Amendment treatments ranging from 0 to 50 g kg(-1) were added to the sediment and equilibrated in 0.001 M CaCl2. After equilibration, the treatment supernatants were analyzed for 137Cs+, U, PO4, and other metals. The residual sediments were then extracted overnight using one of the following: 1.0 M NH4Cl, 0.5 M CaCl2, or the Toxicity Characteristic Leaching Procedure (TCLP) extractant. Cesium was strongly sorbed to the contaminated sediments, presumably due to interlayer fixation within native illitic clays. In fact, 137Cs+ was below detection limits in the initial equilibration solutions, the CaCl2 extract, and the TCLP solution, regardless of amendment. Extractants selective for interlayer cations (1.0 M NH4Cl) were necessary to extract measurable levels of 137Cs+. Addition of illitic clays further reduced Cs+ extractability, even when subjected to the aggressive extractants. Zeolite, however, was ineffective in reducing Cs+ mobility when subjected to the aggressive extractants. Hydroxyapatite was less effective than illite at reducing NH4+-extractable Cs+. Hydroxyapatite, and mixtures of HA with illite or zeolite, were highly effective in reducing U extractability in both batch and leaching tests. Uranium immobilization by HA was rapid with similar final U concentrations observed for equilibration times ranging from 1 h to 30 d. The current results demonstrate the effectiveness of soil amendments in reducing the mobility of U and Cs+, which makes in-place immobilization an effective remediation alternative.     

Profenofos residues in wild fish from cotton-growing areas of New South Wales, Australia

The organophosphorus (OP) pesticide profenofos (O-4-bromo-2-chlorophenyl O-ethyl S-propyl phosphorothioate) is used heavily in cotton-growing areas of eastern Australia toward the end of the growing season. European carp (Cyprinus carpio), bony bream (Nematalosa erebi), and mosquitofish (Gambusia holbrooki) were collected from the cotton-growing areas around Wee Waa, New South Wales, to determine the relationship between profenofos residues and acetyl-cholinesterase (AChE) activity in wild fish. Profenofos concentrations in water, sediment, and fish tissue reflected its general level of use; levels in March 1994 were significantly higher than in 1993 and generally decreased in May, 6 wk after cessation of spraying. Residues in carp and bony bream generally correlated with concentrations in water and sediment, although residues in fish tend to persist longer at some sites. Acetylcholinesterase inhibition was a useful indicator of profenofos exposure within a season, particularly if linked with residue measurements. Bony bream and gravid female mosquitofish recovered AChE levels more slowly than carp or nongravid mosquitofish. Recovery in creeks was generally more rapid than in lagoons.     

Sorption of polycyclic aromatic compounds to humic and fulvic acid HPLC column materials

Two different humic acids (HA) and a fulvic acid (FA) were chemically immobilized to a high performance liquid chromatography (HPLC) silica column material. The immobilization was performed by binding amino groups in HA/FA to the free aldehyde group in glutardialdehyde attached to the silica gel. The HPLC column materials were compared with a blank column material made by applying the same procedure but without immobilizing HA or FA. Also, a column was made by binding carbonyl groups in HA to amino groups attached to the silica gel. The humic substances were selected to secure appropriate variation of their structural features. The retention factors of 45 polycyclic aromatic compounds (PAC) to the four columns were determined by HPLC. The advantage of the technique is a large number of compounds can easily be studied. The binding procedure does not appear to cause a drastic selection between the HA molecules. The k' values obtained for the two Aldrich HA columns agree in general reasonably. The retention or sorption of the compounds increased with the size of the PAC and the number of lipophilic substituents, but decreased when polar substituents were present. The PAC retention was much stronger to the two HA columns than to the FA and blank column, both for hydrophobic polycyclic aromatic hydrocarbons (PAH) and the polar PAC. Other factors impacting the PAC binding may be specific interactions with HA and the ionic strength of the aqueous phase. The technique has been applied to do direct determinations of Koc.     

Tillage, intercrop, and controlled drainage-subirrigation influence atrazine, metribuzin, and metolachlor loss

Atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) and metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide] have been found with increasing occurrence in rivers and streams. Their continued use will require changes in agricultural practices. We compared water quality from four crop-tillage treatments: (i) conventional moldboard plow (MB), (ii) MB with ryegrass (Lolium multiflorum Lam.) intercrop (IC), (iii) soil saver (SS), and (iv) SS + IC; and two drainage control treatments, drained (D) and controlled drainage-subirrigation (CDS). Atrazine (1.1 kg a.i. ha-1), metribuzin [4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazine-5(4H)-one] (0.5 kg a.i. ha-1), and metolachlor (1.68 kg a.i. ha-1) were applied preemergence in a band over seeded corn (Zea mays L.) rows. Herbicide concentration and losses were monitored from 1992 to spring 1995. Annual herbicide losses ranged from < 0.3 to 2.7% of application. Crop-tillage treatment influenced herbicide loss in 1992 but not in 1993 or 1994, whereas CDS affected partitioning of losses in most years. In 1992, SS + IC reduced herbicide loss in tile drains and surface runoff by 46 to 49% compared with MB. The intercrop reduced surface runoff, which reduced herbicide transport. Controlled drainage-subirrigation increased herbicide loss in surface runoff but decreased loss through tile drainage so that total herbicide loss did not differ between drainage treatments. Desethyl atrazine [6-chloro-N-(1-methylethyl)-1,3,5-triazine-2,4-diamine] comprised 7 to 39% of the total triazine loss.     

Bioavailability of biosolids molybdenum to corn

This study was part of a larger effort to generate field data appropriate to the assessment of biosolids molybdenum (Mo) risk to ruminants. Corn (Zea mays L.) is an important component of cattle diet, and is a logical crop for biosolids amendment owing to its high N requirement. Paired soil and corn stover samples archived from two unique field experiments were analyzed to quantify the relationship (uptake coefficient, UC) between stover Mo and soil Mo load. Both studies used biosolids with total Mo concentrations typical of modern materials. Data from long-term (continuous corn) plots in Fulton County, IL confirm expected low Mo accumulation by corn stover, even at very high biosolids loads and soil Mo loads estimated to be near 18 kg Mo ha(-1). Uptake slopes were actually negative, but USEPA protocol would assign UC values of 0.001. Data from plots in Minnesota also suggested essentially no correlations between stover Mo and soil Mo loads for continuous corn. However, greater Mo accumulation in corn grown following soybean [Glycine max (L.) Merr.] suggests the possibility of enhanced Mo bioavailability to corn in corn-soybean rotations. Nevertheless, molybdenosis risk to cattle consuming corn stover produced on biosolids-amended land is small as stover Mo concentrations were always low and stover Cu to Mo ratios exceeded 2:1, which avoids molybdenosis problems.     

Laboratory degradation studies of bentazone, dichlorprop, MCPA, and propiconazole in Norwegian soils

Laboratory degradation studies were performed in Norwegian soils using two commercial formulations (Tilt and Triagran-P) containing either propiconazole alone or a combination of bentazone, dichlorprop, and MCPA. These soils included a fine sandy loam from Hole and a loam from Kroer, both of which are representative of Norwegian agricultural soils. The third soil was a highly decomposed organic material from the Froland forest. A fourth soil from the Skuterud watershed was used only for propiconazole degradation. After 84 d, less than 0.1% of the initial MCPA concentration remained in all three selected soils. For dichlorprop, the same results were found for the fine sandy loam and the organic-rich soil, but in the loam, 26% of the initial concentration remained. After 84 d, less than 0.1% of the initial concentration of bentazone remained in the organic-rich soil, but in the loam and the fine sandy loam 52 and 69% remained, respectively. Propiconazole was shown to be different from the other pesticides by its persistence. Amounts of initial concentration remaining varied from 40, 70, and 82% in the reference soils after 84 d for the organic-rich soil, fine sandy loam, and loam, respectively. The organic-rich soil showed the highest capacity to decompose all four pesticides. The results from the agricultural soils and the Skuterud watershed showed that the persistence of propiconazole was high. Pesticide degradation was approximated to first-order kinetics. Slow rates of degradation, where more than 50% of the pesticide remained in the soil after the 84-d duration of the experiment, did not fit well with first-order kinetics.     

Effects of alum and aluminum chloride on phosphorus runoff from swine manure

Phosphorus (P) runoff from fields fertilized with swine (Sus scrofa domesticus) manure may contribute to eutrophication. The objective of this study was to evaluate the effect of aluminum sulfate (alum) and aluminum chloride applications to swine manure on P runoff from small plots cropped to tall fescue (Festuca arundinacea Shreb.). There were six treatments in this study: (i) unfertilized control plots, (ii) untreated manure, (iii) manure with alum at 215 mg Al L(-1), (iv) manure with aluminum chloride at 215 mg Al L(-1), (v) manure with alum at 430 mg Al L(-1), and (vi) manure with aluminum chloride at 430 mg Al L(-1). Manure application rates were equivalent to approximately 125 kg N ha(-1). Alum and aluminum chloride additions lowered soluble reactive phosphorus (SRP) levels from about 130 mg P L(-1) to approximately 30 mg P L(-1) at low rates. At high rates, SRP levels in swine manure were around 1 mg P L(-1). Soluble reactive P concentrations in runoff were 5.50, 3.66, 3.00, 0.87, 0.87, and 0.55 mg P L(-1), for normal manure, low alum, low aluminum chloride, high alum, high aluminum chloride, and unfertilized control plots, respectively. Hence, high alum and aluminum chloride reduced SRP concentrations in runoff by 84% and were not statistically different from SRP concentrations in runoff from unfertilized control plots. These data indicate that treating swine manure with alum or aluminum chloride could result in significant reductions in nonpoint-source P runoff.     

Cadmium content of wheat grain from a long-term field experiment with sewage sludge

Grain Cd concentrations were determined in the wheat (Triticum aestivum L.) cultivars Soissons, Brigadier, and Hereward grown in 1994,1996, and 1999, respectively, in soils of a long-term field experiment to which sewage sludges contaminated with Zn, Cu, Ni, or Cr had previously been added. Soil pore water soluble Cd and free Cd2+ increased linearly with increasing total soil Cd (R2=0.82 and 0.84, respectively; P<0.001). Similarly, soil pore water free Cd2+ increased linearly with increasing soil pore water soluble Cd (R2=0.98; P<0.001). There was no evidence of a plateau in soil pore water Cd concentrations with increasing soil Cd concentrations. Grain Cd concentrations were significantly correlated with total soil Cd (P<0.001), soil pore water Cd (P<0.001), and free Cd2+ (P<0.001). A slight curvilinear relationship between grain Cd and soil Cd was apparent, but there was no plateau, even at the maximum soil Cd concentration of about 2.7 mg kg(-1). The relationship between soil pore water Cd and grain Cd was linear for all three cultivars. The slopes were in the order 1994 > 1996 > 1999, with more Cd being taken up into the grain by Soissons grown in 1994, and least by Hereward grown in 1999. For Soissons, Cd concentration in the grain greater than the EU limit (0.24 mg kg(-1) dry wt.) occurred at soil Cd less than the current UK limit of 3 mg kg(-1) for soils receiving sewage sludge. In contrast, for Brigadier and Hereward, grain Cd concentrations were near to and less than the EU limit, respectively, at soil Cd concentrations of 3 mg kg(-1).     

Bioavailability of biosolids molybdenum to soybean grain

Legumes grown in biosolids-amended soils and then fed to ruminants can represent problematic sources of molybdenum (Mo), but few field data are available to quantify the risk. We used a set of fields amended to high cumulative biosolids Mo loads (>18 kg ha(-1)) over 27 yr to generate additional data. Soybean [Glycine max (L.) Merr.] was grown on 29 fields (pH values>6.8) amended to a wide range of soil Mo loads. Soybean grain harvested from each field was analyzed for Mo and the concentrations regressed against soil Mo loads estimated from actual soil Mo concentrations in the 0- to 15-cm depth. Slopes of such linear regressions represent uptake coefficients (UC values) used by the USEPA to assess risk of biosolids Mo to ruminants fed forage grown on biosolids-amended land. The UC value for all 29 fields was estimated as 1.66, which agrees with the few soybean grain data in the literature. The UC value, however, is well below a conservative UC value of 4, recently recommended for all fresh legume materials fed to cattle. Soybean grain can contain high concentrations of Mo (>10 mg kg(-1)) and have low (<2:1) Cu to Mo ratios, which can exacerbate molybdenosis problems in cattle. However, soybean grain normally constitutes only -10% of dairy cattle diet, and other constituents (e.g., corn grain, stover, mineral supplements) are sufficient, or can be manipulated, to control molybdenosis.     

Enzymatic characterization of organic phosphorus in animal manure

Information on the forms of P present in animal manure may improve our ability to manage manure P. In most investigations of manure P composition, only inorganic and total P are determined, and the difference between them is assigned as organic P. In this study, we explored the possibility of identifying and quantifying more specific organic P forms in animal manure with orthophosphate-releasing enzymes. Pig (Sus scrofa) manure and cattle (Bos taurus) manure were first sequentially fractionated into water-soluble P, NaHCO3-soluble P, NaOH-soluble P, HCl-soluble P, and residual P. The fractions were separately incubated with wheat phytase, alkaline phosphatase, nuclease P1, nucleotide pyrophosphatase, or their combinations. The released orthophosphate was determined by a molybdate blue method. Part of the organic P in those fractions could be identified by the enzymatic treatments as phytate (i.e., 39% for pig manure and 17% for cattle manure in water-soluble organic P), simple phosphomonoesters (i.e., 43% for pig manure and 15% for cattle manure in NaOH-soluble organic P), nucleotide-like phosphodiesters (2-12%), and nucleotide pyrophosphate (0-4%). Our data indicate that the enzymatic treatment is an effective approach to identify and quantify the organic P forms present in animal manures.