Copper and zinc speciation in a biosolids-amended, semiarid grassland soil.

Predicting trace-metal solid-phase speciation changes associated with long-term biosolids land application is important for understanding and improving environmental quality. Biosolids were surface-applied (no incorporation; 0, 2.5, 5, 10, 21, and 30 Mg ha) to a semiarid grassland in 1991 (single application) and 2002 (repeated application). In July 2003, soils were obtained from the 0- to 8-, 8- to15-, and 15- to 30-cm depths in all plots. Using soil pH, soluble anion and cation concentrations from 0.01 mol L CaCl extractions, dissolved organic C (DOC) content, and an estimate of solid phase humic and fulvic acids present, Cu and Zn associated with minerals, hydrous ferric oxides (HFO), organically complexed, electrostatically bound to organic matter (OM), or DOC phases was modeled using Visual Minteq. Scanning electron microscopy and energy-dispersive X-ray analysis (SEM-EDXRA) was also used to identify solid-phase metal associations present in single and repeated biosolids-amended soils. Based on soil solution chemistry in all depths, as modeled using Visual Minteq, >90% of the Cu and >95% of the Zn from the single or repeated biosolids-applied soils were sorbed electrostatically or as mono- or bidentate solid-phase OM complexes. Up to 10 and 5% of the Cu and Zn, respectively, was associated with HFO, with negligible amounts associated with DOC. The SEM-EDXRA of clay-sized separates from all soil depths led to direct observation of Fe-Cu and Fe-Zn associations. Results implied that after surface-applying biosolids either once or twice with up to 30 Mg ha, some shifts occurred in phases controlling Cu and Zn solubility, but solution concentrations remained below drinking water standards.

Drinking water treatment residuals: a review of recent uses.

Coagulants such as alum [Al2(SO4)3 x 14H2O], FeCl3, or Fe2(SO4)3 are commonly used to remove particulate and dissolved constituents from water supplies in the production of drinking water. The resulting waste product, called water-treatment residuals (WTR), contains precipitated Al and Fe oxyhydroxides, resulting in a strong affinity for anionic species. Recent research has focused on using WTR as cost-effective materials to reduce soluble phosphorus (P) in soils, runoff, and land-applied organic wastes (manures and biosolids). Studies show P adsorption by WTR to be fast and nearly irreversible, suggesting long-term stable immobilization of WTR-bound P. Because excessive WTR application can induce P deficiency in crops, effective application rates and methods remain an area of intense research. Removal of other potential environmental contaminants [ClO4-, Se(+IV and +VI), As(+III and +V), and Hg] by WTR has been documented, suggesting potential use of WTR in environmental remediation. Although the creation of Al plant toxicity and enhanced Al leaching are concerns expressed by researchers, these effects are minimal at circumneutral soil pH conditions. Radioactivity, trace element levels, and enhanced Mn leaching have also been cited as potential problems in WTR usage as a soil supplement. However, these issues can be managed so as not to limit the beneficial use of WTR in controlling off-site P losses to sensitive water bodies or reducing soil-extractable P concentrations.

Infrequent composted biosolids applications affect semi-arid grassland soils and vegetation.

Monitoring of repeated composted biosolids applications is necessary for improving beneficial reuse program management strategies, because materials will likely be reapplied to the same site at a future point in time. A field trial evaluated a single and a repeated composted biosolids application in terms of long-term (13-14 years) and short-term (2-3 years) effects, respectively, on soil chemistry and plant community in a Colorado semi-arid grassland. Six composted biosolids rates (0, 2.5, 5, 10, 21, 30 Mg ha(-1)) were surface applied in a split-plot design study with treatment (increasing compost rates) as the main factor and co-application time (1991, or 1991 and 2002) as the split factor applications. Short- and long-term treatment effects were evident in 2004 and 2005 for soil 0-8 cm depth pH, EC, NO(3)-N, NH(4)-N, total N, and AB-DTPA soil Cd, Cu, Mo, Zn, P, and Ba. Soil organic matter increases were still evident 13 and 14 years following composted biosolids application. The repeated composted biosolids application increased soil NO(3)-N and NH(4)-N and decreased AB-DTPA extractable Ba as compared to the single composted biosolids application in 2004; differences between short- and long-term applications were less evident in 2005. Increasing biosolids rates resulted in increased native perennial grass cover in 2005. Plant tissue Cu, Mo, Zn, and P concentrations increased, while Ba content decreased depending on specific plant species and year. Overall, the lack of many significant negative effects suggests that short- or long-term composted biosolids application at the rates studied did not adversely affect this semi-arid grassland ecosystem.

Fate of biosolids trace metals in a dryland wheat agroecosystem.

Biosolids land application for beneficial reuse applies varying amounts of trace metals to soils. Measuring plant-available or total soil metals is typically performed to ensure environmental protection, but these techniques do not quantify which soil phases play important roles in terms of metal release or attenuation. This study assessed the distribution of Cd, Cr, Cu, Mo, Ni, Pb, and Zn associated with soluble/exchangeable, specifically adsorbed/carbonate-bound, amorphous Mn hydroxyoxide-bound, amorphous Fe hydroxyoxide-bound, organically complexed, and residual inorganic phases. Biosolids were applied every 2 yr from 1982 to 2002 (except in 1998) at rates of 0, 6.7, 13.4, 26.8, and 40.3 dry Mg biosolids ha(-)(1) to 3.6- by 17.1-m plots. In 2003, 0- to 20-cm and 20- to 60-cm soil depths were collected and subjected to 4 mol L(-1) HNO(3) digestion and sequential extraction. Trace metals were concentrated in the 0- to 20-cm depth, with no significant observable downward movement using 4 mol L(-1) HNO(3) or sequential extraction. The sequential extraction showed nearly all measurable Cd present in relatively mobile forms and Cr, Cu, Mo, Ni, Pb, and Zn present in more resistant phases. Biosolids application did not affect Cd or Cr fractionation but did increase relatively immobile Cu, Mo, and Zn phases and relatively mobile Cu, Ni, and Pb pools. The mobile phases have not contributed to significant downward metal movement. Long-term, repeated biosolids applications at rates considered several times greater than agronomic levels should not significantly contribute to downward metal transport and ground water contamination for soils under similar climatic conditions, agronomic practices, and histories.

Biosolids impact soil phosphorus accountability, fractionation, and potential environmental risk.

Biosolids land application rates are typically based on crop N requirements but can lead to soil P accumulation. The Littleton/Englewood, Colorado, wastewater treatment facility has supported biosolids beneficial-use on a dryland wheat-fallow agroecosystem site since 1982, with observable soil P concentration increases as biyearly repeated biosolids applications increased from 0, 6.7, 13, 27, to 40 Mg ha(-1). The final study year was 2003, after which P accountability, fractionation, and potential environmental risk were assessed. Between 93 and 128% of biosolids-P added was accounted for when considering conventional tillage soil displacement, grain removal, and soil adsorption. The Fe-P fraction dominated all soil surface P fractions, likely due to an increase in amorphous Fe-oxide because Fe2(SO4)3 was added at the wastewater treatment facility inflow for digester H2S reduction. The Ca-P phase dominated all soil subsurface P fractions due to calcareous soil conditions. A combination of conventional tillage, drought from 1999 to 2003, and repeated and increasing biosolids application rates may have forced soil surface microorganism dormancy, reduction, or mortality; thus, biomass P reduction was evident. Subsurface biomass P was greater than surface biomass, possibly due to protection against environmental and anthropogenic variables or to increased dissolved organic carbon inputs. Even given years of biosolids application, the soil surface had the ability to sorb additional P as determined by shaking the soil in an excessive P solution. Biosolids-application regulations based on the Colorado Phosphorus Index would not impede current site practices. Proper monitoring, management, and addition of other best management practices are needed for continued assurance that P movement off-site does not become a major issue.

Biosolids affect soil barium in a dryland wheat agroecosystem.

In December 2003, the USEPA released an amended list of 15 "candidate pollutants for exposure and hazard screening" with regard to biosolids land application, including Ba. Therefore, we decided to monitor soil Ba concentrations from a dryland wheat (Triticum aestivum L.)-fallow agroecosystem experiment. This experiment received 10 biennial biosolids applications (1982-2003) at rates from 0 to 26.8 dry Mg ha(-1) per application year. The study was conducted on a Platner loam (Aridic Paleustoll), approximately 30 km east of Brighton, CO. Total soil Ba, as measured by 4 M HNO(3), increased with increasing biosolids application rate. In the soil-extraction data from 1988 to 2003, however, we observed significant (P < 0.10) linear or exponential declines in ammonium bicarbonate-diethylenetriaminepentaacetic acid (AB-DTPA) extractable Ba concentrations as a function of increasing biosolids application rates. This was observed in 6 of 7 and 3 of 7 yr for the 0- to 20- and 20- to 60-cm soil depths, respectively. Results suggest that while total soil Ba increased as a result of biosolids application with time, the mineral form of Ba was present in forms not extractable with AB-DTPA. Scanning electron microscopy using energy dispersive spectroscopy verified soil Ba-S compounds in the soil surface, probably BaSO(4). Wet chemistry sequential extraction suggested BaCO(3) precipitation was increasing in the soil subsurface. Our research showed that biosolids application may increase total soil Ba, but soil Ba precipitates are insoluble and should not be an environmental concern in similar soils under similar climatic and management conditions.

Soil properties affecting wheat yields following drilling-fluid application.

Oil and gas drilling operations use drilling fluids (mud) to lubricate the drill bit and stem, transport formation cuttings to the surface, and seal off porous geologic formations. Following completion of the well, waste drilling fluid is often applied to cropland. We studied potential changes in soil compaction as indicated by cone penetration resistance, pH, electrical conductivity (EC(e)), sodium adsorption ratio (SAR), extractable soil and total straw and grain trace metal and nutrient concentrations, and winter wheat (Triticum aestivum L. 'TAM 107') grain yield following water-based, bentonitic drilling-fluid application (0-94 Mg ha(-1)) to field test plots. Three methods of application (normal, splash-plate, and spreader-bar) were used to study compaction effects. We measured increasing SAR, EC(e), and pH with drilling-fluid rates, but not to levels detrimental to crop production. Field measurements revealed significantly higher compaction within areas affected by truck travel, but also not enough to affect crop yield. In three of four site years, neither drilling-fluid rate nor application method affected grain yield. Extractions representing plant availability and plant analyses results indicated that drilling fluid did not significantly increase most trace elements or nutrient concentrations. These results support land application of water-based bentonitic drilling fluids as an acceptable practice on well-drained soils using controlled rates.

Plant and soil responses to biosolids application following forest fire.

Soil stability and revegetation is a great concern following forest wildfires. Biosolids application might enhance revegetation efforts and enhance soil stability. In May 1997, we applied Metro Wastewater Reclamation District (Denver, CO, USA) composted biosolids at rates of 0, 5, 10, 20, 40, and 80 Mg ha(-1) to a severely burned, previously forested site near Buffalo Creek, CO to improve soil C and N levels and help establish eight native, seeded grasses. The soils on the site belong to the Sphinx series (sandy-skeletal, mixed, frigid, shallow Typic Ustorthents). Vegetation and soils data were collected for four years following treatment. During the four years following treatment, total plant biomass ranged from approximately 50 to 230 g m(-2) and generally increased with increasing biosolids application. The percentage of bare ground ranged from 4 to 58% and generally decreased with increasing biosolids rate. Higher rates of biosolids application were associated with increased concentrations of N, P, and Zn in tissue of the dominant plant species, streambank wheatgrass [Elymus lanceolatus (Scribn. & J.G. Sm) Gould subsp. lanceolatus], relative to the unamended, unfertilized control. At two months following biosolids application (1997), total soil C and N at soil depths of 0 to 7.5, 7.5 to 15, and 15 to 30 cm showed significant (P < 0.05) linear increases (r2 > 0.88) as biosolids rate increased. The surface soil layer also showed this effect one year after application (1998). For Years 2 through 4 (1999-2001) following treatment, soil C and N levels declined but did not show consistent trends. The increase in productivity and cover resulting from the use of biosolids can aid in the rehabilitation of wildfire sites and reduce soil erosion in ecosystems similar to the Buffalo Creek area.

Phosphorus retention mechanisms of a water treatment residual.

Water treatment residuals (WTRs) are a by-product of municipal drinking water treatment plants and can have the capacity to adsorb tremendous amounts of P. Understanding the WTR phosphorus adsorption process is important for discerning the mechanism and tenacity of P retention. We studied P adsorbing mechanism(s) of an aluminum-based [Al2(SO4)3 x 14H2O] WTR from Englewood, CO. In a laboratory study, we shook mixtures of P-loaded WTR for 1 to 211 d followed by solution pH analysis, and solution Ca, Al, and P analysis via inductively coupled plasma atomic emission spectroscopy. After shaking periods, we also examined the solids fraction by X-ray diffraction (XRD) and electron microprobe analysis using wavelength dispersive spectroscopy (EMPA-WDS). The shaking results indicated an increase in pH from 7.2 to 8.2, an increase in desorbed Ca and Al concentrations, and a decrease in desorbed P concentration. The pH and desorbed Ca concentration increases suggested that CaCO3 controlled Ca solubility. Increased desorbed Al concentration may have been due to Al(OH)4 formation. Decreased P content, in conjunction with the pH increase, was consistent with calcium phosphate formation or precipitation. The system appeared to be undersaturated with respect to dicalcium phosphate (DCP; CaHPO4) and supersaturated with respect to octacalcium phosphate [OCP; Ca4H(PO4)3 x 2.5H2O]. The Ca and Al increases, as well as OCP formation, were supported by MINTEQA2 modeling. The XRD and EMPA-WDS results for all shaking times, however, suggested surface P chemisorption as an amorphous Al-P mineral phase.

Solution chemistry influence on metal mobility in biosolids-amended soils.

Many studies have implicated dissolved organic carbon (DOC) as an important contributor to the elevated mobility of trace metals in soils amended with biosolids. Few of these studies, however, have quantified both DOC and metal concentrations. We completed laboratory leaching column studies on a dryland Platner loam (fine, smectitic, mesic Aridic Paleustoll) and an irrigated Osgood sand (loamy, mixed, mesic Arenic Ustollic Haplargid), both with a history of biosolids application. The soils were neutral to slightly alkaline in pH prior to amendment. We performed an additional application of biosolids to one set of columns in the laboratory at a rate of 28 Mg ha(-1) to investigate the effect of time following application on metal mobility. The effect of electrolyte concentration was studied by using both distilled water and simulated irrigation water. Biosolids application increased both DOC and Cu in the column effluents resulting in a positive correlation between Cu and DOC across application treatments for both soils. Both Cu and Pb were mobilized under conditions of low electrical conductivity (EC). This may be the result of the release of a strong metal-binding component of DOC under these conditions. Conversely, Zn mobility was positively correlated with EC, suggesting that either cation exchange or the formation of inorganic complexes influences Zn mobility. Anodic stripping voltammetry measurements indicated that only a small percentage of the total dissolved metals existed as free ions or inorganic complexes; the remainder appears to be complexed to DOC.

Biosolids applications affect runoff water quality following forest fire.

Soil erosion and nutrient losses are great concerns following forest wildfires. Biosolids application might enhance revegetation efforts while reducing soil erodibility. Consequently, we applied Denver Metro Wastewater District composted biosolids at rates of 0, 40, and 80 Mg ha(-1) to a severely burned, previously forested site near Buffalo Creek, CO to increase plant cover and growth. Soils were classified as Ustorthents, Ustochrepts, and Haploborols. Simulated rainfall was applied for 30 min at a rate of 100 mm h(-1) to 3- x 10-m paired plots. Biosolids application rates did not significantly affect mean total runoff (p < 0.05). Sediment concentrations were significantly greater (p < 0.05) from the control plots compared with the plots that had received the 80 Mg biosolids ha(-1) rate. Biosolids application rate had mixed effects on water-quality constituents; however, concentrations of all runoff constituents for all treatment rates were below levels recommended for drinking water standards, except Pb. Biosolids application to this site increased plant cover, which should provide erosion control.