In situ treatment of metals in contaminated soils with phytate

Batch experiments were conducted to evaluate the ability of various forms of phytate, the hexaphosphoric form of myo-inositol (IP6), to immobilize U, Ni, and other inorganic contaminants in soils and sediments. A Ca-phytate precipitate (Ca(n)-IP6), dodeca sodium-phytate (Na12-IP6), and hydroxyapatite (HA) were added to contaminated soil at rates of 0, 10, 25, and 50 g kg(-1) and equilibrated in 0.001 M CaCl2. The samples were then centrifuged, the solution pH was measured, and the supernatants were filtered prior to analysis for dissolved organic carbon (DOC), U, Ni, P, and other inorganic contaminants, such as As, Cr, Se, and Pb. The residual sediments were air-dried prior to characterization by analytical electron microscopy and extraction with the Toxicity Characteristic Leaching Procedure (TCLP). The solubility of several metals (e.g., U, Pb, Cu) increased with increasing Na12-IP6 when compared with the nonamended control. In some cases immobilization was observed at the lowest Na12-IP6 application rate (10 g kg(-1)) with an increase in solubility observed at the higher rates, demonstrating the importance of metal to ligand ratio. In contrast, Ca(n)-IP6 and HA decreased the solubility of U, Ni, Al, Pb, Ba, Co, Mn, and Zn. For example, soluble U decreased from 2242 to 76 microg kg(-1) and Ni from 58 to 9.6 mg kg with the Ca(n)-IP6 addition, similar to the results observed for HA. Arsenic and Se solubility increased for HA and both forms of IP6, but to a much greater degree for Na12-IP6, suggesting that the increase in pH observed for HA and Na12-IP6, combined with added competition from PO4 and IP6 for sorption sites, resulted in the release of sorbed oxyanion contaminants. The analytical electron microscopy results indicated that metals such as U and Ni were closely associated with secondary Al-rich precipitates in the HA-treated soils, rather than unreacted HA. The analytical electron microscopy results were less definitive for the Ca(n)-IP6-treated soil, although the residual P-containing material was enriched in Al, with lesser amounts of U and Ni.     

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.     

Future directions of meteorology related to air-quality research

Meteorology is one of the major factors contributing to air-pollution episodes. More accurate representation of meteorological fields has been possible in recent years through the use of remote sensing systems, high-speed computers and fine-mesh meteorological models. Over the next 5-20 years, better meteorological inputs for air quality studies will depend on making better use of a wealth of new remotely sensed observations in more advanced data assimilation systems. However, for fine mesh models to be successful, parameterizations used to represent physical processes must be redesigned to be more precise and better adapted for the scales at which they will be applied. Candidates for significant overhaul include schemes to represent turbulence, deep convection, shallow clouds, and land-surface processes. Improvements in the meteorological observing systems, data assimilation and modeling, coupled with advancements in air-chemistry modeling, will soon lead to operational forecasting of air quality in the US. Predictive capabilities can be expected to grow rapidly over the next decade. This will open the way for a number of valuable new services and strategies, including better warnings of unhealthy atmospheric conditions, event-dependent emissions restrictions, and now casting support for homeland security in the event of toxic releases into the atmosphere.     

Immobilization of cesium-137 and uranium in contaminated sediments using soil amendments

Batch and dynamic leaching methods were used to evaluate the effectiveness of hydroxyapatite (HA), illite, and zeolite, alone and in combination, as soil additives for reducing the migration of cesium-137 (137Cs+) and uranium (U) from contaminated sediments. Amendment treatments ranging from 0 to 50 g kg(-1) were added to the sediment and equilibrated in 0.001 M CaCl2. After equilibration, the treatment supernatants were analyzed for 137Cs+, U, PO4, and other metals. The residual sediments were then extracted overnight using one of the following: 1.0 M NH4Cl, 0.5 M CaCl2, or the Toxicity Characteristic Leaching Procedure (TCLP) extractant. Cesium was strongly sorbed to the contaminated sediments, presumably due to interlayer fixation within native illitic clays. In fact, 137Cs+ was below detection limits in the initial equilibration solutions, the CaCl2 extract, and the TCLP solution, regardless of amendment. Extractants selective for interlayer cations (1.0 M NH4Cl) were necessary to extract measurable levels of 137Cs+. Addition of illitic clays further reduced Cs+ extractability, even when subjected to the aggressive extractants. Zeolite, however, was ineffective in reducing Cs+ mobility when subjected to the aggressive extractants. Hydroxyapatite was less effective than illite at reducing NH4+-extractable Cs+. Hydroxyapatite, and mixtures of HA with illite or zeolite, were highly effective in reducing U extractability in both batch and leaching tests. Uranium immobilization by HA was rapid with similar final U concentrations observed for equilibration times ranging from 1 h to 30 d. The current results demonstrate the effectiveness of soil amendments in reducing the mobility of U and Cs+, which makes in-place immobilization an effective remediation alternative.     

Effects of temporary starvation on the survival,and on subsequent feeding and growth,of oyster (Crassostrea gigas) larvae

Larvae of oysters, Crassostrea gigas, were maintained without food for 1 to 8 d after fertilization, and fed daily thereafter. There was little difference in survival and growth between controls and larvae kept without food for 2 or 3 d. Survival and growth rates were depressed in larvae starved for 4 or 5 d. For larvae starved for 6 to 8 d, survival was negligible or nil; even those larvae which survived the starvation period died later in the presence of food, apparently because of impaired digestion. Therefore, food availability in the first few days after spawning appears to be of paramount importance to the successful recruitment of Pacific oysters.     

Building capacity with demand-driven partnerships: a case study of Partners for Water and Sanitation

Multi-stakeholder partnerships emerged from the 2002 Johannesburg World Summit on Sustainable Development (WSSD) as a new vehicle for progressing toward the Millennium Development Goals (MDGs) by aligning the interests of businesses, governments and civil society to leverage the impact of their interventions. The water and sanitation sector boasts the largest number of such partnerships, including the demand-driven capacity-building partnership Partners for Water and Sanitation (PAWS), a product of the WSSD and a premier UK partnership for sustainable development. Through its partnership network, PAWS has access to the entire UK water industry, which they assign to capacity-building projects in Africa on a demand-driven basis. Though the supply of partners is generally strong, the demand for their assistance is variable. This paper examines the efficacy of demand-driven capacity building partnerships at achieving the water and sanitation MDGs, presenting a case study of the PAWS partnership and using it as a framework for discussion of the supply–demand dynamics that influence the scope, scale and ultimate impact of such partnerships.     

Fate of arsenic compounds in poultry litter upon land application

The use of the organic As compound, roxarsone, as an antibiotic additive to poultry feed continues to raise concern over potential negative environmental impacts. Total As concentration in poultry litter can reach >40 mg kg⁻¹ and both roxarsone and its mineralization product As(V) have been identified in poultry litters (PL). To investigate the fate of these As species upon land application of PL we conducted two studies. In the first, an Orangeburg soil (Ultisol from the Atlantic Coastal Plain) was spiked with either 20 mg kg⁻¹ As(V) or roxarsone and incubated at 10% moisture content for 4 months. Exchangeable As was determined periodically by extraction with 0.1 M PO₄. Both As(V) and roxarsone displayed similar desorption; initially, approximately 70% of added As was ligand exchangeable and this decreased to 35% after 4 months incubation, presumably due to either slow sorption reactions or a change in solid phase speciation of As to less exchangeable forms. In the second study, various manipulations of two PL samples were applied to the Orangeburg soil at realistic field application rates. The treatments were wet to 10% moisture content and water soluble As, Cu and organic carbon (DOC) was measured over 30 days. Arsenic and Cu solubility were highest from the dried litter samples. Ashing of the PLs decreased soluble As and Cu, presumably because of the loss of organic matter from the ashed litter and subsequent decrease in DOC. Application of leachates from either PL resulted in higher concentrations of soluble As and Cu than when the soil was amended with equivalent concentrations of soluble As and Cu dissolved in DI H₂O. We hypothesize that the increased levels of DOC from the PL treatments enhance As and Cu solubility through competitive sorption and complexation, respectively. In fact, As and Cu solubility was correlated to DOC levels in the amended soil extracts. Even though land application of PL introduced relatively low concentrations of As and Cu to soil it appeared that other soluble constituents of PL significantly enhanced As and Cu solubility.