Assessment of metal availability in smelter soil using earthworms and chemical extractions

Chemical immobilization is a relatively inexpensive in situ remediation method that reduces soil contaminant solubility, but the ability of this remediation treatment to reduce heavy metal bioavailability and ecotoxicity to soil invertebrates has not been evaluated. Our objectives were to (i) assess the ability of chemical immobilization amendments (municipal sewage sludge biosolids and rock phosphate) to reduce metal bioavailability and toxicity in a toxic metal-contaminated smelter soil and (ii) evaluate soil extraction methods using Ca(NO3)2 solution or ion-exchange membranes coated with diethylenetriaminepentaacetic acid (DTPA) as surrogate measures of metal bioavailability and ecotoxicity. We treated a soil contaminated by Zn and Pb milling and smelting operations and an uncontaminated control soil with lime-stabilized municipal biosolids (LSB), rock phosphate (RP), or anaerobically digested municipal biosolids (SS) and evaluated lethality of the remediated soils to earthworm (Eisenia fetida Savigny). Lime-stabilized municipal biosolids was the only remediation amendment to successfully immobilize lethal levels of Zn in the smelter soil (14-d cumulative mortality < or = 15%). Calcium nitrate-extractable Zn in the lethal Zn smelter soil-amendment combinations was 11.5 to 18.2 mmol/kg, compared with the nonlethal LSB amended soil (0.62 mmol/kg). The Ca(NO3)2-extractable Zn-based median lethal concentration (LC50) of 6.33 mmol/kg previously developed in Zn-spiked artificial soils was applicable in the remediated smelter soils despite a 14-fold difference in total Zn concentration. Chelating ion-exchange membrane uptake among the soils was highly variable (mean CV = 39%) compared with the Ca(NO3)2-extraction (mean CV = 1.9%) and not well related to earthworm toxicity.     

Trace element speciation in poultry litter

Trace elements are added to poultry feed for disease prevention and enhanced feed efficiency. High concentrations are found in poultry litter (PL), which raises concerns regarding trace element loading of soils. Trace metal cation solubility from PL may be enhanced by complexation with dissolved organic carbon (DOC). Mineralization of organo-As compounds may result in more toxic species such as As(III) and As(V). Speciation of these elements in PL leachates should assist in predicting their fate in soil. Elemental concentrations of 40 PL samples from the southeastern USA were determined. Water-soluble extractions (WSE) were fractionated into hydrophobic, anionic, and cationic species with solid-phase extraction columns. Arsenic speciation of seven As species, including the main As poultry feed additives, roxarsone (ROX; 3-nitro-4-hydroxyphenylarsonic acid) and p-arsanilic acid (p-ASA; 4-aminophenylarsonic acid), was performed by ion chromatography-inductively coupled plasma-mass spectrometry (IC-ICP-MS). Total As concentrations in the litter varied from 1 to 39 mg kg(-1), averaging 16 mg kg(-1). Mean total Cu, Ni, and Zn concentrations were 479, 11, and 373 mg kg(-1), respectively. Copper and Ni were relatively soluble (49 and 41% respectively) while only 6% of Zn was soluble. Arsenic was highly soluble with an average of 71% WSE. Roxarsone was the major As species in 50% of PL samples. However, the presence of As(V) as the major species in 50% of the PL samples indicates that mineralization of ROX had occurred. The high solubility of As from litter and its apparent ready mineralization to inorganic forms coupled with the large quantity of litter that is annually land-applied in the USA suggests a potential detrimental effect on soil and water quality in the long term.     

Major and trace elements of selected pedons in the USA

Few studies of soil geochemistry over large geographic areas exist, especially studies encompassing data from major pedogenic horizons that evaluate both native concentrations of elements and anthropogenically contaminated soils. In this study, pedons (n = 486) were analyzed for trace (Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Zn) and major (Al, Ca, Fe, K, Mg, Na, P, Si, Ti, Zr) elements, as well as other soil properties. The objectives were to (i) determine the concentration range of selected elements in a variety of U.S. soils with and without known anthropogenic additions, (ii) illustrate the association of elemental source and content by assessing trace elemental content for several selected pedons, and (iii) evaluate relationships among and between elements and other soil properties. Trace element concentrations in the non-anthropogenic dataset (NAD) were in the order Mn > (Zn, Cr, Ni, Cu) > (Pb, Co) > (Cd, Hg), with greatest mean total concentrations for the Andisol order. Geometric means by horizon indicate that trace elements are concentrated in surface and/or B horizons over C horizons. Median values for trace elements are significantly higher in surface horizons of the anthropogenic dataset (AD) over the NAD. Total Al, Fe, cation exchange capacity (CEC), organic C, pH, and clay exhibit significant correlations (0.56, 0.74, 0.50, 0.31, 0.16, and 0.30, respectively) with total trace element concentrations of all horizons of the NAD. Manganese shows the best inter-element correlation (0.33) with these associated total concentrations. Total Fe has one of the strongest relationships, explaining 55 and 30% of the variation in total trace element concentrations for all horizons in the NAD and AD, respectively.     

METHODOLOGIES FOR CALIBRATION AND PREDICTIVE ANALYSIS OF A WATERSHED MODEL1

ABSTRACT: The use of a fitted parameter watershed model to address water quantity and quality management issues requires that it be calibrated under a wide range of hydrologic conditions. However, rarely does model calibration result in a unique parameter set. Parameter nonuniqueness can lead to predictive nonuniqueness. The extent of model predictive uncertainty should be investigated if management decisions are to be based on model projections. Using models built for four neighboring watersheds in the Neuse River Basin of North Carolina, the application of the automated parameter optimization software PEST in conjunction with the Hydrologic Simulation Program Fortran (HSPF) is demonstrated. Parameter nonuniqueness is illustrated, and a method is presented for calculating many different sets of parameters, all of which acceptably calibrate a watershed model. A regularization methodology is discussed in which models for similar watersheds can be calibrated simultaneously. Using this method, parameter differences between watershed models can be minimized while maintaining fit between model outputs and field observations. In recognition of the fact that parameter nonuniqueness and predictive uncertainty are inherent to the modeling process, PEST's nonlinear predictive analysis functionality is then used to explore the extent of model predictive uncertainty.     

Importance of Sediment–Water Interactions in Coeur d’Alene Lake,Idaho, USA: Management Implications

A field study at Coeur dAlene Lake, Idaho, USA, was conducted between October 1998 and August 2001 to examine the potential importance of sediment–water interactions on contaminant transport and to provide the first direct measurements of the benthic flux of dissolved solutes of environmental concern in this lake. Because of potential ecological effects, dissolved zinc and orthophosphate were the solutes of primary interest. Results from deployments of an in situ flux chamber indicated that benthic fluxes of dissolved Zn and orthophosphate were comparable in magnitude to riverine inputs. Tracer analyses and benthic-community metrics provided evidence that solute benthic flux were diffusion-controlled at the flux-chamber deployment sites. That is, effects of biomixing (or bioturbation) and ground-water interactions did not strongly influence benthic flux. Remediation efforts in the river might not produce desired water-quality effects in the lake because imposed shifts in concentration gradients near the sediment–water interface would generate a benthic feedback response. Therefore, development of water-quality models to justify remediation strategies requires consideration of contaminant flux between the water column and underlying sediment in basins that have been affected by long-term (decadal) anthropogenic activities.     

An environmental threshold for degree of phosphorus saturation in sandy soils

There is critical need for a practical indicator to assess the potential for phosphorus (P) movement from a given site to surface waters, either via surface runoff or subsurface drainage. The degree of phosphorus saturation (DPS), which relates a measure of P already adsorbed by a soil to its P adsorption capacity, could be a good indicator of that soil's P release capability. Our primary objective was to find a suitable analytical protocol for determining DPS and to examine the possibility of defining a threshold DPS value for Florida's sandy soils. Four farmer-owned dairy sprayfields were selected within the Suwannee River basin and soil profiles were randomly obtained from each site, as well as from adjacent unimpacted sites. The soil samples were divided either by horizon or depth, and DPS was determined for each soil sample using ammonium-oxalate (DPS(Ox)), Mehlich-1 (DPS(M1)), and Mehlich-3 (DPS(M3)) extracts. All methods of DPS calculations were linearly related to one another (r2 > 0.94). Relationships between water-soluble P and DPS indicate that the respective change points are: DPS(Ox) = 20%, DPS(M1) = 20%, and DPS(M3) = 16%. These relationships include samples from Ap, E, and Bt horizons, and various combinations thereof, suggesting that DPS values can be used as predictors of P loss from a soil irrespective of the depth of the soil within a profile. Taking into consideration the change points, confidence intervals, agronomic soil test values, and DPS values from other studies, we suggest replacing Mehlich-1 P values in the Florida P Index with the three DPS categories (DPS(M1) = <30, 30-60, and >60%) to assign different P loss ratings in the P Index.     

Agricultural drainage ditches mitigate phosphorus loads as a function of hydrological variability

Phosphorus (P) loading from nonpoint sources, such as agricultural landscapes, contributes to downstream aquatic ecosystem degradation. Specifically, within the Mississippi watershed, enriched runoff contributions have far-reaching consequences for coastal water eutrophication and Gulf of Mexico hypoxia. Through storm events, the P mitigation capacity of agricultural drainage ditches under no-till cotton was determined for natural and variable rainfall conditions in north Mississippi. Over 2 yr, two experimental ditches were sampled monthly for total inorganic P concentrations in baseflow and on an event-driven basis for stormflows. Phosphorus concentrations, Manning's equations with a range of roughness coefficients for changes in vegetative densities within the ditches, and discharge volumes from Natural Resources Conservation Service dimensionless hydrographs combined to determine ranges in maximum and outflow storm P loads from the farms. Baseflow regressions and percentage reductions with P concentrations illustrated that the ditches alternated between being a sink and source for dissolved inorganic P and particulate P concentrations throughout the year. Storm event loads resulted in 5.5% of the annual applied fertilizer to be transported into the drainage ditches. The ditches annually reduced 43.92 +/- 3.12% of the maximum inorganic effluent P load before receiving waters. Agricultural drainage ditches exhibited a fair potential for P mitigation and thus warrant future work on controlled drainage to improve mitigation capacity.     

A Multi‐Scale Analysis of Single‐Family Residential Water Use in the Phoenix Metropolitan Area

Studies that evaluate determinants of residential water demand typically use data from a single spatial scale. Although household‐scale data are preferred, especially when econometric models are used, researchers may be limited to aggregate data. There is little, if any, empirical analysis to assess whether spatial scale may lead to ecological fallacy problems in residential water use research. Using linear mixed‐effects models, we compare the results for the relationship of single‐family water use with its determinants using data from the household and census tract scales in the city of Phoenix. Model results between the household and census tract scale are similar suggesting the ecological fallacy may not be significant. Common significant determinants on these two spatial scales include household size, household income, house age, pool size, irrigable lot size, precipitation, and temperature. We also use city/town scale data from the Phoenix metropolitan area to parameterize the linear mixed‐effects model. The difference in the parameter estimates of those common variables compared to the first two scales indicates there is spatial heterogeneity in the relationship between single‐family water use and its determinants among cities and towns. The negative relationship between single‐family house density and residential water use suggests that residential water consumption could be reduced through coordination of land use planning and water demand management.     

Decreased Runoff Response to Precipitation,Little Missouri River Basin,Northern Great Plains,USA

High variability in precipitation and streamflow in the semiarid northern Great Plains causes large uncertainty in water availability. This uncertainty is compounded by potential effects of future climate change. We examined historical variability in annual and growing season precipitation, temperature, and streamflow within the Little Missouri River Basin and identified differences in the runoff response to precipitation for the period 1976‐2012 compared to 1939‐1975 (n = 37 years in both cases). Computed mean values for the second half of the record showed little change (<5%) in annual or growing season precipitation, but average annual runoff at the basin outlet decreased by 22%, with 66% of the reduction in flow occurring during the growing season. Our results show a statistically significant (p < 0.10) 27% decrease in the annual runoff response to precipitation (runoff ratio). Surface‐water withdrawals for various uses appear to account for <12% of the reduction in average annual flow volume, and we found no published or reported evidence of substantial flow reduction caused by groundwater pumping in this basin. Results of our analysis suggest that increases in monthly average maximum and minimum temperatures, including >1°C increases in January through March, are the dominant driver of the observed decrease in runoff response to precipitation in the Little Missouri River Basin.     

Degradation and removal methods of antibiotics from aqueous matrices--a review

Over the past few years, antibiotics have been considered emerging pollutants due to their continuous input and persistence in the aquatic ecosystem even at low concentrations. They have been detected worldwide in environmental matrices, indicating their ineffective removal from water and wastewater using conventional treatment methods. To prevent this contamination, several processes to degrade/remove antibiotics have been studied. This review addresses the current state of knowledge concerning the input sources, occurrence and mainly the degradation and removal processes applied to a specific class of micropollutants, the antibiotics. In this paper, different remediation techniques were evaluated and compared, such as conventional techniques (biological processes, filtration, coagulation, flocculation and sedimentation), advanced oxidation processes (AOPs), adsorption, membrane processes and combined methods. In this study, it was found that ozonation, Fenton/photo-Fenton and semiconductor photocatalysis were the most tested methodologies. Combined processes seem to be the best solution for the treatment of effluents containing antibiotics, especially those using renewable energy and by-products materials.