Bioleaching of metals from spent lithium ion secondary batteries using Acidithiobacillus ferrooxidans

Bioleaching of spent lithium ion secondary batteries, containing LiCoO2, was attempted in this investigation. The present study was carried out using chemolithotrophic and acidophilic bacteria Acidithiobacillus ferrooxidans, which utilized elemental sulfur and ferrous ion as the energy source to produce metabolites like sulfuric acids and ferric ion in the leaching medium. These metabolites helped dissolve metals from spent batteries. Bio-dissolution of cobalt was found to be faster than lithium. The effect of initial Fe(II) concentration, initial pH and solid/liquid (w/v) ratio during bioleaching of spent battery wastes were studied in detail. Higher Fe(II) concentration showed a decrease in dissolution due co-precipitation of Fe(III) with the metals in the residues. The higher solid/liquid ratio (w/v) also affected the metal dissolution by arresting the cell growth due to increased metal concentration in the waste sample. An EDXA mapping was carried out to compare the solubility of both cobalt and lithium, and the slow dissolution rate was clearly found from the figures.     

Perspectives and limits for cement kilns as a destination for RDF

RDF, the high calorific value fraction of MSW obtained by conventional separation systems, can be employed in technological plants (mainly cement kilns) in order to obtain a useful energy recovery. It is interesting and important to evaluate this possibility within the general framework of waste-to-energy solutions. The solution must be assessed on the basis of different aspects, namely: technological features and clinker characteristics; local atmospheric pollution; the effects of RDF used in cement kilns on the generation of greenhouse gases; the economics of conventional solid fuels substitution and planning perspectives, from the point of view of the destination of RDF and optimal cement kiln policy. The different experiences of this issue throughout Europe are reviewed, and some applications within Italy are also been considered. The main findings of the study are that the use of RDF in cement kilns instead of coal or coke offers environmental benefits in terms of greenhouse gases, while the formation of conventional gaseous pollutants is not a critical aspect. Indeed, the generation of nitrogen oxides can probably be lower because of lower flame temperatures or lower air excess. The presence of chlorinated micro-pollutants is not influenced by the presence of RDF in fuel, whereas depending on the quality of the RDF, some problems could arise compared to the substituted fuel as far as heavy metals are concerned, chiefly the more volatile ones.     

Estimated occupational risk from bioaerosols generated during land application of class B biosolids

Some speculate that bioaerosols from land application of biosolids pose occupational risks, but few studies have assessed aerosolization of microorganisms from biosolids or estimated occupational risks of infection. This study investigated levels of microorganisms in air immediately downwind of land application operations and estimated occupational risks from aerosolized microorganisms. In all, more than 300 air samples were collected downwind of biosolids application sites at various locations within the United States. Coliform bacteria, coliphages, and heterotrophic plate count (HPC) bacteria were enumerated from air and biosolids at each site. Concentrations of coliforms relative to Salmonella and concentrations of coliphage relative to enteroviruses in biosolids were used, in conjunction with levels of coliforms and coliphages measured in air during this study, to estimate exposure to Salmonella and enteroviruses in air. The HPC bacteria were ubiquitous in air near land application sites whether or not biosolids were being applied, and concentrations were positively correlated to windspeed. Coliform bacteria were detected only when biosolids were being applied to land or loaded into land applicators. Coliphages were detected in few air samples, and only when biosolids were being loaded into land applicators. In general, environmental parameters had little impact on concentrations of microorganisms in air immediately downwind of land application. The method of land application was most correlated to aerosolization. From this large body of data, the occupational risk of infection from bioaerosols was estimated to be 0.78 to 2.1%/yr. Extraordinary exposure scenarios carried an estimated annual risk of infection of up to 34%, with viruses posing the greatest threat. Risks from aerosolized microorganisms at biosolids land application sites appear to be lower than those at wastewater treatment plants, based on previously reported literature.     

Farm factors associated with reducing Cryptosporidium loading in storm runoff from dairies

A systems approach was used to evaluate environmental loading of Cryptosporidium oocysts on five coastal dairies in California. One aspect of the study was to determine Cryptosporidium oocyst concentrations and loads for 350 storm runoff samples from dairy high use areas collected over two storm seasons. Selected farm factors and beneficial management practices (BMPs) associated with reducing the Cryptosporidium load in storm runoff were assessed. Using immunomagnetic separation (IMS) with direct fluorescent antibody (DFA) analysis, Cryptosporidium oocysts were detected on four of the five farms and in 21% of storm runoff samples overall. Oocysts were detected in 59% of runoff samples collected near cattle less than 2 mo old, while 10% of runoff samples collected near cattle over 6 mo old were positive. Factors associated with environmental loading of Cryptosporidium oocysts included cattle age class, 24 h precipitation, and cumulative seasonal precipitation, but not percent slope, lot acreage, cattle stocking number, or cattle density. Vegetated buffer strips and straw mulch application significantly reduced the protozoal concentrations and loads in storm runoff, while cattle exclusion and removal of manure did not. The study findings suggest that BMPs such as vegetated buffer strips and straw mulch application, especially when placed near calf areas, will reduce environmental loading of fecal protozoa and improve stormwater quality. These findings are assisting working dairies in their efforts to improve farm and ecosystem health along the California coast.     

Occurrence and fate of pesticides in four contrasting agricultural settings in the United States

Occurrence and fate of 45 pesticides and 40 pesticide degradates were investigated in four contrasting agricultural settings--in Maryland, Nebraska, California, and Washington. Primary crops included corn at all sites, soybeans in Maryland, orchards in California and Washington, and vineyards in Washington. Pesticides and pesticide degradates detected in water samples from all four areas were predominantly from two classes of herbicides--triazines and chloroacetanilides; insecticides and fungicides were not present in the shallow ground water. In most samples, pesticide degradates greatly exceeded the concentrations of parent pesticide. In samples from Nebraska, the parent pesticide atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine] was about the same concentration as the degradate, but in samples from Maryland and California atrazine concentrations were substantially smaller than its degradate. Simazine [6-chloro-N,N'-diethyl-1,3,5-triazine-2,4-diamine], the second most detected triazine, was detected in ground water from Maryland, California, and Washington. Metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide] rarely was detected without its degradates, and when they were detected in the same sample metolachlor always had smaller concentrations. The Root-Zone Water-Quality Model was used to examine the occurrence and fate of metolachlor at the Maryland site. Simulations accurately predicted which metolachlor degradate would be predominant in the unsaturated zone. In analyses of relations among redox indicators and pesticide variance, apparent age, concentrations of dissolved oxygen, and excess nitrogen gas (from denitrification) were important indicators of the presence and concentration of pesticides in these ground water systems.     

Whole-stream response to nitrate loading in three streams draining agricultural landscapes

Physical, chemical, hydrologic, and biologic factors affecting nitrate (NO3(-)) removal were evaluated in three agricultural streams draining orchard/dairy and row crop settings. Using 3-d "snapshots" during biotically active periods, we estimated reach-level NO3(-) sources, NO3(-) mass balance, in-stream processing (nitrification, denitrification, and NO3(-) uptake), and NO3(-) retention potential associated with surface water transport and ground water discharge. Ground water contributed 5 to 11% to stream discharge along the study reaches and 8 to 42% of gross NO3(-) input. Streambed processes potentially reduced 45 to 75% of ground water NO3(-) before discharge to surface water. In all streams, transient storage was of little importance for surface water NO3(-) retention. Estimated nitrification (1.6-4.4 mg N m(-2) h(-1)) and unamended denitrification rates (2.0-16.3 mg N m(-2) h(-1)) in sediment slurries were high relative to pristine streams. Denitrification of NO3(-) was largely independent of nitrification because both stream and ground water were sources of NO3(-). Unamended denitrification rates extrapolated to the reach-scale accounted for <5% of NO3(-) exported from the reaches minimally reducing downstream loads. Nitrate retention as a percentage of gross NO3(-) inputs was >30% in an organic-poor, autotrophic stream with the lowest denitrification potentials and highest benthic chlorophyll a, photosynthesis/respiration ratio, pH, dissolved oxygen, and diurnal NO3(-) variation. Biotic processing potentially removed 75% of ground water NO3(-) at this site, suggesting an important role for photosynthetic assimilation of ground water NO3(-) relative to subsurface denitrification as water passed directly through benthic diatom beds.     

Adsorption-desorption characteristics of mercury in paddy soils of China

Mercury (Hg) has received considerable attention because of its association with various human health problems. Adsorption-desorption behavior of Hg at contaminated levels in two paddy soils was investigated. The two representative soils for rice production in China, locally referred to as a yellowish red soil (YRS) and silty loam soil (SLS) and classified as Gleyi-Stagnic Anthrosols in FAO/UNESCO nomenclature, were respectively collected from Jiaxin County and Xiasha District of Hangzhou City, Zhejiang Province. The YRS adsorbed more Hg(2+) than the SLS. The characteristics of Hg adsorption could be described by the simple Langmuir adsorption equation (r2 = 0.999 and 0.999, P < 0.01, respectively, for the SLS and YRS). The maximum adsorption values (Xm) that were obtained from the simple Langmuir model were 111 and 213 mg Hg(2+) kg(-1) soil, respectively, for the SLS and YRS. Adsorption of Hg(2+) decreased soil pH by 0.75 unit for the SLS soil and 0.91 unit for the YRS soil at the highest loading. The distribution coefficient (kd) of Hg in the soil decreased exponentially with increasing Hg(2+) loading. After five successive desorptions with 0.01 mol L(-1) KCl solution (pH 5.4), 0 to 24.4% of the total adsorbed Hg(2+) in the SLS soil was desorbed and the corresponding value of the YRS soil was 0 to 14.4%, indicating that the SLS soil had a lower affinity for Hg(2+) than the YRS soil at the same Hg(2+) loading. Different mechanisms are likely involved in Hg(2+) adsorption-desorption at different levels of Hg(2+) loading and between the two soils.     

Effect of nitrogen fertilizer application on growing season soil carbon dioxide emission in a corn-soybean rotation

Nitrogen application can have a significant effect on soil carbon (C) pools, plant biomass production, and microbial biomass C processing. The focus of this study was to investigate the short-term effect of N fertilization on soil CO(2) emission and microbial biomass C. The study was conducted from 2001 to 2003 at four field sites in Iowa representing major soil associations and with a corn (Zea mays L.)-soybean (Glycine max L. Merr.) rotation. The experimental design was a randomized complete block with four replications of four N rates (0, 90, 180, and 225 kg ha(-1)). In the corn year, season-long cumulative soil CO(2) emission was greatest with the zero N application. There was no effect of N applied in the prior year on CO(2) emission in the soybean year, except at one of three sites, where greater applied N decreased CO(2) emission. Soil microbial biomass C (MBC) and net mineralization in soil collected during the corn year was not significantly increased with increase in N rate in two out of three sites. At all sites, soil CO(2) emission from aerobically incubated soil showed a more consistent declining trend with increase in N rate than found in the field. Nitrogen fertilization of corn reduced the soil CO(2) emission rate and seasonal cumulative loss in two out of three sites, and increased MBC at only one site with the highest N rate. Nitrogen application resulted in a reduction of both emission rate and season-long cumulative emission of CO(2)-C from soil.     

Empirical models based on the universal soil loss equation fail to predict sediment discharges from Chesapeake Bay catchments

The Universal Soil Loss Equation (USLE) and its derivatives are widely used for identifying watersheds with a high potential for degrading stream water quality. We compared sediment yields estimated from regional application of the USLE, the automated revised RUSLE2, and five sediment delivery ratio algorithms to measured annual average sediment delivery in 78 catchments of the Chesapeake Bay watershed. We did the same comparisons for another 23 catchments monitored by the USGS. Predictions exceeded observed sediment yields by more than 100% and were highly correlated with USLE erosion predictions (Pearson r range, 0.73-0.92; p < 0.001). RUSLE2-erosion estimates were highly correlated with USLE estimates (r = 0.87; p < 001), so the method of implementing the USLE model did not change the results. In ranked comparisons between observed and predicted sediment yields, the models failed to identify catchments with higher yields (r range, -0.28-0.00; p > 0.14). In a multiple regression analysis, soil erodibility, log (stream flow), basin shape (topographic relief ratio), the square-root transformed proportion of forest, and occurrence in the Appalachian Plateau province explained 55% of the observed variance in measured suspended sediment loads, but the model performed poorly (r(2) = 0.06) at predicting loads in the 23 USGS watersheds not used in fitting the model. The use of USLE or multiple regression models to predict sediment yields is not advisable despite their present widespread application. Integrated watershed models based on the USLE may also be unsuitable for making management decisions.     

Influence of prairie restoration on CT-measured soil pore characteristics

Restored prairies are expected to improve soil physical properties, yet little is known about the extent of change to soil properties and how rapidly these changes take place. The objective of this study was to compare effects of prairie restoration on computed tomography (CT)-measured pore parameters. Undisturbed soil cores (76 mm diam. by 76 mm long) from native prairie (NP), restored prairie (RP), conservation reserve program (CRP), and no-till corn (Zea mays L.)-soybean (Glycine max (L.) Merr.; CS) sites were collected with six replicates from the 0- to 40-cm depth in 10-cm increments. Five CT images were acquired from each soil core using a medical CT scanner with 0.2 by 0.2 mm pixel resolution with 0.5 mm slice thickness, and then images were analyzed. Soil bulk density and hydraulic conductivity (K(sat)) were also measured. Soils under NP, RP, CRP, and CS areas had 83, 43, 48, and 26 pores on a 2500 mm(2) area, respectively, for the 0- to 40-cm depth. The number of pores, number of macropores (>1000 microm diam.), macroporosity, mesoporosity (200-1000 microm diam.), and fractal dimension were significantly higher and pore circularity was lower for NP, RP, and CRP than the CS treatment. The CT-measured mesoporosity and macroporosity of the CS treatment were 20 and 18% of the values for the NP site. CT-measured number of pores and macropores explained 43 and 40% of the variation for K(sat). The study showed that prairie restoration improves CT-measured soil pore parameters and decreases bulk density which are related to soil water infiltration.