Meta-Analysis of Gypsum Effects on Crop Yields and Chemistry of Soils, Plant Tissues, and Vadose Water at Various Research Sites in the USA.

Gypsum has a long history as a soil amendment. Information on how flue gas desulfurization (FGD) gypsum affects soil, water, and plant properties across a range of climates and soils is lacking. We conducted a meta-analysis using data from 10 field sites in the United States (Alabama, Arkansas, Indiana, New Mexico, North Dakota, Ohio, and Wisconsin). Each site used three rates each of mined and FGD gypsums plus an untreated control treatment. Gypsum rates included a presumed optimal agronomic rate plus one rate lower and one rate higher than the optimal. Gypsum was applied once at the beginning of each study, and then data were collected for 2 to 3 yr. The meta-analyses used response ratios () calculated by dividing the treatment value by the control value for crop yield or for each measured element in plant, soil, and vadose water. These values were tested for their significance with values. Most values varied only slightly from 1.00. Gypsum significantly changed more values from 1.00 for vadose water than for soil or crop tissue in terms of numbers of elements affected (11 for water, 7 for soil, and 8 for crop tissue). The highest value for soil was 1.57 (Ca) which was similar for both mined and FGD gypsum, for crop tissue was 1.46 (Sr) for mined gypsum, and for vadose water was 4.22 (S) for FGD gypsum. The large increase in Ca and S is often a desired response to gypsum application. Lowest values occurred in crop tissue for Mg (0.89) with FGD gypsum and for Ni (0.92 or 0.93) with both gypsums. Although some sites showed crop yield responses to gypsum, the overall mean values for mined gypsum (0.987) and for FGD gypsum (1.00) were not significantly different from 1.00 in this short-term study.

Effects of flue gas desulfurization and mined gypsums on soil properties and on hay and corn growth in eastern ohio.

Gypsum (CaSO·2HO) is a quality source of Ca and S and has various beneficial uses that can improve agricultural production. This study was conducted to compare rates of flue gas desulfurization (FGD) gypsum and commercially available agricultural (i.e., mined) gypsum as soil amendments on soils typical of eastern Ohio or western Pennsylvania. Two field experiments were conducted, one involving a mixed grass hay field and the other corn ( L.). Gypsum was applied once at rates of 0.2, 2.0, and 20 Mg ha and a seventh treatment was a zero rate control. Corn grain yields response to gypsum was mixed with significant differences between low and high gypsum rates in 2010 but not between gypsum and no gypsum treatments. In the hay study, the low and intermediate gypsum rates generally did not result in any significant changes compared with the control treatment. At the high rate of 20 Mg ha, the following results were observed for the hay study: (i) both gypsums generally increased Ca, S, and soluble salts (electrical conductivity) in the topsoil and subsoil, when compared with the control; (ii) the FGD gypsum decreased Mg in soil when compared with all other treatments, and mined gypsum decreased Mg when compared with the control; and (iii) there were few effects on soil concentrations of trace elements, including Hg. Also at the high application rate, hay yield for the first cutting (May) in 2009 and 2010 was significantly less for mined and FGD gypsum compared with the control, but increased yields in subsequent cutting resulted in no significant treatment differences in total annual hay yield for 2008, 2009, or 2010 or cumulative yield for 2008 to 2010. Overall, for the hay study, the absence of significant soil chemical effects for the intermediate gypsum rate and the decrease in soil Mg concentrations for the high gypsum rate indicate that an application rate of approximately 2.0 Mg ha would be optimal for this soil.

Adsorption of arsenic(V) onto fly ash: a speciation-based approach.

Arsenic (As) poses a significant water quality problem and challenge for the environmental engineers and scientists in the world. The large volume of coal fly ash produced around the world is a potentially significant anthropogenic source of arsenic. Currently the leaching behavior of arsenic from fly ash is not well understood. Batch methods were used in this study to investigate arsenic leaching using a raw ash, and arsenic adsorption using a clean, washed ash. Experimental results indicated that pH had a significant effect on arsenic leaching or adsorption. Between pH 3 and 7, less arsenic was in the dissolved phase. When pH was less than 3 or greater than 7, increasing amounts of arsenic were leached or desorbed from fly ash. The leaching and adsorption behavior of arsenic was interpreted with the speciation of surface sites and arsenic. In a new approach, a speciation-based model was developed to quantify the arsenic adsorption as a function of pH and surface acidity parameters. This work is important in offering insight into the leaching mechanism of arsenic from coal fly ash, and providing a robust model based upon specific, measurable parameters to quantify arsenic adsorption by other solid media in addition to fly ash.

The role of ammonia on mercury leaching from coal fly ash.

The Federal Clean Air Interstate Rule issued in March 2005 will result in many power plants employing ammonia-based technologies to control NO(x) emission. The Clean Air Mercury Rule, issued at the same time, will encourage many power plants to use various technologies to remove mercury from flue gas, generating fly ashes that contain elevated concentrations of mercury. Ammonia forms relatively strong complexes with mercury compared to most other cationic elements and, therefore, may change the leaching characteristics of mercury. Understanding the impact of ammonia on the leaching of mercury from fly ash is critical in predicting the potential environmental impact of future fly ash. Batch methods were used to investigate the ammonia impact on mercury leaching from fly ash under different pH conditions. The results indicated that mercury leaching without external ammonia addition is not significant. However, ammonia addition increased mercury leaching in the alkaline pH range, due to the formation of less adsorbable mercury-ammonia complexes. Washed ash released more mercury than the raw ash if the ammonia concentration is the same, mainly due to the dissolution of some ash components during washing which exposed more mercury on ash surface. Mercury adsorption data indicated that more than 90% of available mercury was adsorbed by fly ash even in the presence of 1000 mg l(-1) ammonia addition.

The leaching characteristics of selenium from coal fly ashes.

The leaching characteristics of selenium from several bituminous and subbituminous coal fly ashes under different pH conditions were investigated using batch methods. Results indicated that pH had a significant effect on selenium leaching from bituminous coal ash. The minimum selenium leaching occurred in the pH range between 3 and 4, while the maximum selenium leaching occurred at pH 12. The release of selenium from subbituminous coal ashes was very low for the entire experimental pH range, possibly due to the high content of calcium which can form hydration or precipitation products as a sink for selenium. The adsorption results for different selenium species indicated that Se(VI) was hardly adsorbable on either bituminous coal ashes or subbituminous coal ashes at any pH. However, Se(IV) was highly adsorbed by bituminous coal ashes under acidic pH conditions and was mostly removed by subbituminous coal ashes across the entire pH range. This result suggests that the majority of selenium released from the tested fly ashes was Se(IV). A speciation-based model was developed to simulate the adsorption of Se(IV) on bituminous coal fly ash, and the pH-independent adsorption constants of HSeO3* and SeO3 2* were determined. The modeling approach is useful for understanding and predicting the release process of selenium from fly ash.

Quantifying the availability and the stability of trace cationic elements in fly ash.

For adsorption-desorption controlled leaching processes, the total leachable mass and the adsorption constant are parameters representing the availability and the stability of trace elements in solid media. With these parameters, one can predict the leaching behavior of trace elements from solids under various pH and solid-to-liquid ratio conditions. An approach was developed in this paper to determine these parameters for model elements Cu(II), Cd(II), and Ni(II) in fly ash. This approach consists of a batch equilibrium titration, a batch equilibrium leaching with and without target element addition, and mathematical modeling. Results indicated that the adsorption constant of a trace element can be determined by modeling the adsorption ratio of the added element to the system as a function of pH. Results also indicated that the trace element originally present in fly ash had similar adsorption-desorption behavior as that added externally. By modeling the batch leaching data with and without external element addition, the total leachable mass and adsorption constant of the target element can be determined simultaneously. The total leachable mass is in agreement with experimental data from 50mM EDTA extraction.

Impacts of pH and ammonia on the leaching of Cu(II) and Cd(II) from coal fly ash.

Many coal-fired power plants are implementing ammonia-based technologies to reduce NO(x) emissions. Excess ammonia in the flue gas often deposits on the coal fly ash. Ammonia can form complexes with many heavy metals and change the leaching characteristics of these metals. This research tends to develop a fundamental understanding of the ammonia impact on the leaching of some heavy metals, exemplified by Cu(II) and Cd(II), under different pH conditions. Batch results indicated that the adsorption is the main mechanism controlling Cu(II) and Cd(II) leaching, and high concentrations of ammonia (>5,000 mg/l) can increase the release of Cu(II) and Cd(II) in the alkaline pH range. Based on the chemical reactions among fly ash, ammonia, and heavy metal ion, a mathematical model was developed to quantify effects of pH and ammonia on metal adsorption. The adsorption constants (logK) of Cu(2+), Cu(OH)(+), Cu(OH)(2), and Cu(NH(3))(m)(2+) for the fly ash under investigation were respectively 6.0, 7.7, 9.6, and 2.9. For Cd(II), these constants were respectively 4.3, 6.9, 8.8, and 2.6. Metal speciation calculations indicated that the formation of less adsorbable metal-ammonia complexes decreased metal adsorption, therefore enhanced metal leaching.

Laboratory investigation of Hg release from flue gas desulfurization products.

Flue gas desulfurization (FGD) is a process applied to remove acid deposition precursors from the coal combustion air stream. This process also removes mercury (Hg) resulting in accumulation of this element in FGD produced solids. This project investigated Hg release from FGD materials to the air and water. Hg concentrations in the synthetic leaching precipitation procedure extracts, designed to simulate rainwater pH conditions, were in general <10 ng L(-1). Unlike coal fly ash, which has been found to adsorb Hg from the air, FGD materials were found to release Hg to the air over time with the addition of water a dominant environmental factor promoting release. The chemistry of the atmosphere to which the FGD materials were exposed (i.e., air Hg concentration and presence of oxidants), as well as that of the material (i.e., salts removed), was found to influence the magnitude of emissions. Although this work showed a component of the Hg captured by the FGD process could be released to the air under laboratory conditions, the potential for release under disposal and beneficial use conditions needs to be determined.

Selenium and arsenic speciation in fly ash from full-scale coal-burning utility plants.

X-ray absorption fine structure spectroscopy has been used to determine directly the oxidation states and speciation of selenium and arsenic in 10 fly ash samples collected from full-scale utility plants. Such information is needed to assess the health risk posed by these elements in fly ash and to understand their behavior during combustion and in fly ash disposal options, such as sequestration in tailings ponds. Selenium is found predominantly as Se(IV) in selenite (SeO3(2-)) species, whereas arsenic is found predominantly as As(V) in arsenate (AsO4(3-)) species. Two distinct types of selenite and arsenate spectra were observed depending upon whether the fly ash was derived from eastern U.S. bituminous (Fe-rich) coals or from western subbituminous or lignite (Ca-rich) coals. Similar spectral details were observed for both arsenic and selenium in the two different types of fly ash, suggesting that the postcombustion behavior and capture of both of these elements are likely controlled by the same dominant element or phase in each type of fly ash.