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.     

The relationship between microbial carbon and the resource quality of soil carbon

The biological health of soil is an important aspect of soil quality because of the many critical functions performed by organisms in soil. Various indicators of soil quality have been proposed, but measurements of microbial biomass are most commonly used. During decomposition of plant residues in soil the relative intensities of the O-alkyl-C signal decreases and the alkyl-C signal increases in nuclear magnetic resonance (NMR) spectra. This leads to the suggestion that the alkyl-C to O-alkyl-C ratio of a soil may indicate the degree of decomposition. Consequently, the overall resource quality of soil C as a substrate for heterotrophic microorganisms may be inversely related to the alkyl-C to O-alkyl-C ratio. Our hypothesis is that a relationship exists between the size of the soil microbial community (microbial biomass) and the quality of soil carbon as a resource for microorganisms. New data have been combined with previously published data to show that there was a significant, negative correlation between the biomass C to total C (Cmic, to Corg) ratio and the alkyl-C to O-alkyl-C ratio (p < 0.01), which supports our hypothesis.     

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.     

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.     

Nitrogen input to the Gulf of Mexico

Historical streamflow and concentration data were used in regression models to estimate the annual flux of nitrogen (N) to the Gulf of Mexico and to determine where the nitrogen originates within the Mississippi Basin. Results show that for 1980-1996 the mean annual total N flux to the Gulf of Mexico was 1,568,000 t yr-1. The flux was about 61% nitrate N, 37% organic N, and 2% ammonium N. The flux of nitrate N to the Gulf has approximately tripled in the last 30 years with most of the increase occurring between 1970 and 1983. The mean annual N flux has changed little since the early 1980s, but large year-to-year variations in N flux occur because of variations in precipitation. During wet years the N flux can increase by 50% or more due to flushing of nitrate N that has accumulated in the soils and unsaturated zones in the basin. The principal source areas of N are basins in southern Minnesota, Iowa, Illinois, Indiana, and Ohio that drain agricultural land. Basins in this region yield 1500 to more than 3100 kg N km-2 yr-1 to streams, several times the N yield of basins outside this region.     

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.     

Residents' perceptions of water quality improvements following remediation work in the Pymme's Brook catchment, north London, UK

Residents' perceptions of water quality change following remediation work in the upper Pymme's Brook catchment (north London) were elicited by questionnaire and compared with monitored changes in Escherichia coli count and BMWP (The Biological Monitoring Working Party (BMWP)) score. The wider usefulness of consumer perception surveys was then discussed. Monthly data collected between 1990 and 1996 shows that both E. coli count and BMWP score improved following flushing of the foul sewerage system in 1992, but that only E. coli count improved following the subsequent completion of large-scale remedial engineering works. Local residents were surveyed regarding their awareness of the scheme, and the causes of pollution, together with their perceptions as to the effects of the engineering works and of the resulting water quality improvements. Most respondents selected and ranked indicators in a way that suggested they had an awareness of the significance of various indicators of pollution severity. Following completion of the remediation scheme, residents perceived the watercourse to contain less rubbish and sewage fungus, and to have an improved colour and smell, which corresponds favourably to the monitored improvements. However, respondents' perceptions were found to vary when the study population was sub-divided using a range of parameters. For instance, frequent observers of the brook were most likely to correctly identify sewage as the main form of pollution. These divergent perceptions suggest that there may be considerable difficulties when perception surveys are used to quantify 'benefits' following environmental improvement programmes. Nevertheless, the survey was clearly beneficial in enhancing residents' awareness of their environment and the role of their voice in its management.     

ESF Workshop

Dioxin and PCB monitoring programs for food and feeding stuff in most countries of the world, including many European Countries are currently inadequate. Better control of food production lines and food processing procedures is needed to minimize entry of dioxin to the food chain and will help to avoid dioxin contamination accidents. This would also improve the ability to trace back a possible contamination to its source. European guidelines for monitoring programs should be established to ensure comparable and meaningful results. These guidelines should define the minimum requirements for the design of monitoring programs, analytical methods, and quality assurance. Though data from Northern Europe shows that the general population exposure to dioxin and PCB has decreased during the last ten years these compounds continue to be a risk of accidental contamination of the food chain. The most prominent recent example is the Belgian dioxin contamination of feeding stuff in 1999. The Belgian dioxin contamination was not detected due to dioxin monitoring programs but by their direct biological effects seen in animals. Four other cases of dioxin contamination have been detected in Europe since 1997 due to local monitoring programs. One of them (citrus pulp pellets 1998) was in a much larger scale than the Belgian dioxin contamination. The general population's exposure to dioxins and PCBs is still in the same range (1-4 pg WHO-TEQ/kg body weight and day) as the recently revised WHO tolerable daily intake (TDI). There is concern that short-term high level exposure to dioxins, furans, and PCB may cause biological effects on the human fetal development and further research is required. Further actions to control sources building on considerable advances already made in many countries may need to be supplemented by measures to prevent direct contamination of feeding stuff or food to reduce general population exposure further.     

Radionuclide fluxes at a plant manufacturing dicalcium phosphate for domestic animals

We have studied a phosphate rock plant which produces dicalcium phosphate (DCP), used as a source of calcium and phosphorus for domestic animals. A by-product in the manufacturing process is calcium chloride which is used in the oil industry, the food industry and as road-salt. The objectives of our study were to describe the fluxes of radionuclides from the 238U decay series and to estimate the radiation doses to workers at the plant. The radionuclides in the phosphate rock were found to be in secular radioactive equilibrium with 238U, with an average activity concentration of 837 Bq kg-1. Separation and concentration processes were observed at different stages in the plant. Most of the 226Ra was found in the calcium chloride, while the major part of the 238U, about 950 Bq kg-1, was found in the dicalcium phosphate. The annual occupational effective dose to the workers was found to be below the 1 mSv limit recommended by ICRP (1991a) for the public. This study has shown a good example of an important non-nuclear industry with a high input of natural radionuclides with several conceivable pathways to man.