Prediction of zinc, cadmium, lead, and copper availability to wheat in contaminated soils using chemical speciation, diffusive gradients in thin films, extraction, and isotopic dilution techniques

To predict the availability of metals to plants, it is important to understand both solution- and solid-phase processes in the soil, including the kinetics of metal release from its binding agent (ligand and/or particle). The present study examined the speciation and availability of Zn, Cd, Pb, and Cu in a range of well-equilibrated metal-contaminated soils from diverse sources using several techniques as a basis for predicting metal uptake by plants. Wheat (Triticum aestivum L.) was grown in 13 metal-contaminated soils and metal tissue concentrations (Zn, Cd, Pb, and Cu) in plant shoots were compared with total soil metal concentrations, total soluble metal, and free metal activities (pM2+) in soil pore waters, 0.01 M CaCl2-extractable metal concentrations, E values measured by isotope dilution, and effective metal concentrations, C(E), measured by diffusive gradients in thin films (DGT). In the DGT technique, ions are dynamically removed by their diffusion through a gel to a binding resin, while E values represent the isotopically exchangeable (labile) metal pools. Free metal activities (Zn2+, Cd2+, and Pb2+) in soil pore waters were determined using a Donnan dialysis technique. Plant Zn and Cd concentrations were highly related to C(E), while relationships for Zn and Cd with respect to the other measures of metals in the soils were generally lower, except for CaCl2-extractable Cd. These results suggest that the kinetically labile solid-phase pool of metal, which is included in the DGT measurement, played an important role in Zn and Cd uptake by wheat along with the labile metal in soil solution. Plant Pb concentrations were highly related to both soil pore water concentrations and C(E), indicating that supply from the solid phase may not be so important for Pb. Predictions of Cu uptake by wheat from these soils by the various measures of Cu were generally poor, except surprisingly for total Cu.     

Mineral contents and proximate composition of Pistacia vera kernels

The mineral contents of Pistacia vera kernels were determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The minimum and maximum values of K, P, Ca, Mg, and S elements ranged from 6,333 to 8,064 mg/kg, 3,630 to 5,228 mg/kg, 1,614 to 3,226 mg/kg, 1,716 to 2,402 mg/kg, and 1,417 to 1,825 mg/kg, respectively. In addition, the mean values of Fe, Zn, Cu, Mn, B, Mo, Cr and Ni elements were determined as 42.48, 20.52, 12.81, 7.48, 11.31, 0.106, 0.511 and 1.67 mg/kg, respectively. Ash levels of kernels were found between 2.28 % (Urfa) and 2.79 % (Halebi). In addition, crude oil and protein contents were determined between 48.8 % (Halebi) to 55.3 % (Siirt) and 23.33 % (Uzun) to 27.16 % (Halebi), respectively.     

EPA’s LIMB Development and Demonstration Program

This paper describes and discusses key design features of the retrofit of EPA’s Limestone Injection Multistage Burner (LIMB) system to an operating, wall-fired utility boiler at Ohio Edison’s Edgewater Station, based on the preliminary engineering design. It further describes results of pertinent projects in EPA's LIMB program and shows how these results were used as the basis for the design of the system. The full-scale demonstration is expected to prove the effectiveness and cost of the LIMB concept for use on large-scale utility boilers. To date, a preliminary engineering design for the Edgewater unit has been prepared incorporating the technology developed in smaller-scale studies. The schedule calls for system start-up by March 1987. EPA is engaged in a multiyear program to develop an improved control technology for emission of sulfur and nitrogen oxides from the combustion of fossil fuels. The technology involves staged-flow coal burners and injection of a reactive sorbeht into the furnace to reduce emissions. The program includes fundamental studies of reaction chemistry and kinetics, bench and pilot scale experimental studies, a full-scale demonstration, and economic and applicability studies. It is structured to establish a basis for future public sector commercialization, as well as help in understanding the technology’s controlling factors.     

Variations in pesticide leaching related to land use, pesticide properties, and unsaturated zone thickness

Pesticide leaching through variably thick soils beneath agricultural fields in Morgan Creek, Maryland was simulated for water years 1995 to 2004 using LEACHM (Leaching Estimation and Chemistry Model). Fifteen individual models were constructed to simulate five depths and three crop rotations with associated pesticide applications. Unsaturated zone thickness averaged 4.7 m but reached a maximum of 18.7 m. Average annual recharge to ground water decreased from 15.9 to 11.1 cm as the unsaturated zone increased in thickness from 1 to 10 m. These point estimates of recharge are at the lower end of previously published values, which used methods that integrate over larger areas capturing focused recharge in the numerous detention ponds in the watershed. The total amount of applied and leached masses for five parent pesticide compounds and seven metabolites were estimated for the 32-km2 Morgan Creek watershed by associating each hectare to the closest one-dimensional model analog of model depth and crop rotation scenario as determined from land-use surveys. LEACHM parameters were set such that branched, serial, first-order decay of pesticides and metabolites was realistically simulated. Leaching is predicted to be greatest for shallow soils and for persistent compounds with low sorptivity. Based on simulation results, percent parent compounds leached within the watershed can be described by a regression model of the form e(-depth) (a ln t1/2-b ln K OC) where t1/2 is the degradation half-life in aerobic soils, K OC is the organic carbon normalized sorption coefficient, and a and b are fitted coefficients (R2 = 0.86, p value = 7 x 10(-9)).     

Modelling the mitigation of a hydrogen deflagration in a nuclear waste silo ullage with water fog

During the decommissioning of certain legacy nuclear waste storage plants it is possible that significant releases of hydrogen gas could occur. Such an event could result in the formation of a flammable mixture within the silo ullage and, hence, the potential risk of ignition and deflagration occurring, threatening the structural integrity of the silo. Very fine water mist fogs have been suggested as a possible method of mitigating the overpressure rise, should a hydrogen–air deflagration occur. In the work presented here, the FLACS CFD code has been used to predict the potential explosion overpressure reduction that might be achieved using water fog mitigation for a range of scenarios where a hydrogen–air mixture, of a pre-specified concentration (containing 800 L of hydrogen), uniformly fills a volume located in a model silo ullage space, and is ignited giving rise to a vented deflagration. The simulation results suggest that water fog could significantly reduce the peak explosion overpressure, in a silo ullage, for lower concentration hydrogen–air mixtures up to 20%, but would require very high fog densities to be achieved to mitigate 30% hydrogen–air mixtures.     

Heavy metals intake by cultured mushrooms growing in model system

Micro element and heavy metal contents of mushrooms were determined by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES). It was seen an increase in the heavy metal contents (except Cu and Zn) of the mushrooms until the second dose. A decrease was seen in heavy metal intake of the mushroom in the application of the third dose. The highest accumulation occurred from the upper soils treated with the second dose. Amounts of Cd, Cr, Cu, Pb and Zn, which were accumulated in the mushroom after the application of this dose, were detected as 5.7, 23.1, 75.7, 62.8 and 99.3 ppm, respectively.     

Macro- and microelement contents of some legume seeds

Macro- and microelement contents of legume seeds were determined by ICP-AES. The potassium K contents of seeds ranged between 7,426 mg/kg (Lupinus albus L.) and 16,558 mg/kg (Phaseolus vulgaris L. ssp. sphaericus Mart). In addition, while P contents of seeds changed from 2,719 mg/kg (L. albus L.) to 5,792 mg/kg (Vigna sinensis (L.) Savi), Ca contents ranged at the levels between 1,309 mg/kg (Cicer arietinum L.) and 2,781 mg/kg (L. albus L.). The microelement contents of samples were found to be different depending on several species. The iron levels of samples were determined at the levels between 90.51 mg/kg (Phaseolus mungo L.) and 152.80 mg/kg (P. vulgaris L. ssp. sphaericus Mart). In addition, Zn contents of seeds were found between 31.32 mg/kg (C. arietinum L.) and 44.75 mg/kg (V. sinensis (L.) Savi).     

Apportionment of ambient primary and secondary fine particulate matter during a 2001 summer intensive study at the CMU Supersite and NETL Pittsburgh site

Gaseous and particulate pollutant concentrations associated with five samples per day collected during a July 2001 summer intensive study at the Pittsburgh Carnegie Mellon University (CMU) Supersite were used to apportion fine particulate matter (PM2.5) into primary and secondary contributions using PMF2. Input to the PMF2 analysis included the concentrations of PM2.5 nonvolatile and semivolatile organic material, elemental carbon (EC), ammonium sulfate, trace element components, gas-phase organic material, and NO(x), NO2, and O3 concentrations. A total of 10 factors were identified. These factors are associated with emissions from various sources and facilities including crustal material, gasoline combustion, diesel combustion, and three nearby sources high in trace metals. In addition, four secondary sources were identified, three of which were associated with secondary products of local emissions and were dominated by organic material and one of which was dominated by secondary ammonium sulfate transported to the CMU site from the west and southwest. The three largest contributors to PM2.5 were secondary transported material (dominated by ammonium sulfate) from the west and southwest (49%), secondary material formed during midday photochemical processes (24%), and gasoline combustion emissions (11%). The other seven sources accounted for the remaining 16% of the PM2.5. Results obtained at the CMU site were comparable to results previously reported at the National Energy Technology Laboratory (NETL), located approximately 18 km south of downtown Pittsburgh. The major contributor at both sites was material transported from the west and southwest. Some difference in nearby sources could be attributed to meteorology as evaluated by HYSPLIT model back-trajectory calculations. These findings are consistent with the majority of the secondary ammonium sulfate in the Pittsburgh area being the result of contributions from distant transport, and thus decoupled from local activity involving organic pollutants in the metropolitan area. In contrast, the major local secondary sources were dominated by organic material.     

Growth in the bivalve Yoldia eightsi at Signy Island,Antarctica, determined from internal shell increments and calcium-45 incorporation

The growth rate of the infaunal nuculanid bivalve Yoldia eightsi at Factory Cove, Signy Island, South Orkney Islands (maritime Antarctica), was estimated from internal shell increments and ⁴⁵Ca incorporation of individuals collected monthly from December 1987 to April 1989. Acetate peels of etched shells revealed clear first-order increments, with less well defined, narrower, second-and third-order increments. The first-order increments were assumed to be annual, although there is no independent confirmation of this assumption. Unfortunately abrasion of the umbo region and the small thin shells of Y. eightsi meant that in no case could a complete sequence of increments be measured realiably on any individual shell. Measurements of 1043 first-order increments from 130 shells where a minimum of two consecutive increments could be detected were therefore pooled, and a population growth curve constructed from a Ford-Walford plot. This indicated a slow growth rate, with a maximum shell height of 22.3 mm (equivalent to a shell length of 35.6 mm) being reached at an age >60 yr. The size-frequency distribution of 1521 individuals pooled from winter (July to October) samples revealed a distinct lack of smaller (younger) individuals, possibly reflecting poor recruitment in areas of dense adult populations. The largest shell recovered in the samples was 33.5 mm in length, with an estimated age of 52 yr. Short-term ⁴⁵Ca-incorporation experiments indicated a mean daily rate of growth increment of 3.8 m for individuals of 12 mm shell height, which matches the proposed annual growth rate if growth is assumed to occur for about 150 d each year and the first-order increments are assumed to be annual.     

Degree of phosphorus saturation thresholds in manure-amended soils of alberta

The risk of P losses from agricultural land to surface and ground water generally increases as the degree of soil P saturation increases. A single-point soil P sorption index (PSI) was validated with adsorption isotherm data for determination of the P sorption status of Alberta soils. Soil P thresholds (change points) were then examined for two agricultural soils after eight annual applications of different rates of cattle manure and for three agricultural soils after one application of different rates of cattle manure. Linear relationships were found between soil-test P (STP) levels up to 1000 mg kg(-1) and desorbed P in the five Alberta soils. Weak linear relationships were also found between STP and runoff dissolved reactive phosphorus (DRP) in three of these soils. Change points for the degree of P saturation (DPS) were detected in four of the five soils at 3 to 44% for water-extractable P (WEP) and at 11 to 51% for CaCl(2)-extractable P (CaCl(2)-P). Change points were not found for DPS or runoff DRP. Overall DPS thresholds for the five soils combined were 27% for WEP and 44% for CaCl(2)-P at a critical desorbable-P value of 1 mg L(-1). The corresponding STP levels (44 mg kg(-1) for WEP and 71 mg kg(-1) for CaCl(2)-P) are similar to agronomic thresholds for crops grown on Alberta soils. Soluble P losses in overland flow and leaching may be greater in soils with DPS values that exceed these thresholds than in soils with lower DPS values.