Sulfidation treatment of molten incineration fly ashes with Na2S for zinc, lead and copper resource recovery

The present study focuses on the conversion of heavy metals involved in molten incineration fly ashes to metal sulfides which could be thereafter separated by flotation. The sulfidation treatment was carried out for five molten incineration fly ashes (Fly ash-A to Fly ash-E) by contacting each fly ash with Na(2)S solution for a period of 10 min to 6h. The initial molar ratio of S(2-) to Me(2+) was adjusted to 1.20. The conversion of heavy metals to metal sulfides was evaluated by measuring the S(2-) residual concentrations using an ion selective electrode. The formation of metal sulfides was studied by XRD and SEM-EDS analyses. In the case of Fly ash-A to Fly ash-D, more than 79% of heavy metals of zinc, lead and copper was converted to metal sulfides within the contacting period of 0.5h owing to a fast conversion of metal chlorides to metal sulfides. By contrast, the conversion of about 35% was achieved for Fly ash-E within the same contacting period, which was attributed to a high content of metal oxides. Further, the S(2-) to Me(2+) molar ratio was reduced to 1.00 to minimize Na(2)S consumption and the conversions obtained within the contacting period of 0.5h varied from 76% for Fly ash-D to 91% for Fly ash-C. Finally, soluble salts such as NaCl and KCl were removed during the sulfidation treatment, which brought about a significant enrichment in metals content by a factor varying from 1.5 for Fly ash-D to 4.9 for Fly ash-A.     

Isolation and characterization of 1,2,4-trichlorobenzene mineralizing Bordetella sp. and its bioremediation potential in soil

A soil which has been polluted with chlorinated benzenes for more than 25 years was used for isolation of adapted microorganisms able to mineralize 1,2,4-trichlorobenzene (1,2,4-TCB). A microbial community was enriched from this soil and acclimated in liquid culture under aerobic conditions using 1,2,4-TCB as a sole available carbon source. From this community, two strains were isolated and identified by comparative sequence analysis of their 16S-rRNA coding genes as members of the genus Bordetella with Bordetella sp. QJ2-5 as the highest homological strain and with Bordetella petrii as the closest related described species. The 16S-rDNA of the two isolated strains showed a similarity of 100%. These strains were able to mineralize 1,2,4-TCB within two weeks to approximately 50% in liquid culture experiments. One of these strains was reinoculated to an agricultural soil with low native 1,2,4-TCB degradation capacity to investigate its bioremediation potential. The reinoculated strain kept its biodegradation capability: (14)C-labeled 1,2,4-TCB applied to this inoculated soil was mineralized to about 40% within one month of incubation. This indicates a possible application of the isolated Bordetella sp. for bioremediation of 1,2,4-TCB contaminated sites.     

Biological denitrification of high strength nitrate waste using preadapted denitrifying sludge

Denitrification of synthetic high nitrate waste containing 9032 ppm NO(3)-N (40,000 ppm NO(3)) in a time period of only 6h has been achieved in our previous study using activated sludge. The activated sludge culture was acclimatized by a stepwise increase in the nitrate concentration of synthetic waste. In the present work, studies were carried out on the changing microbial population of the sludge and the physiology of nitrate metabolism during the various stages of adaptation process to high strength synthetic nitrate waste. During the course of adaptation, with an increase in the nitrate concentration, a sharp increase in the number of denitrifiers was found with an equally rapid decrease in the nitrifying community. Two key enzymes involved in the first two steps of the denitrification process were also studied during this period. The results of the study suggest that specific enzyme levels increase as the activated sludge adapts itself to higher nitrate concentrations. Biological denitrification of high nitrate waste is a slow process and to increase the rate of denitrification, parameters such as pH, temperature, C:N and biomass concentration of the process were optimized using orthogonal array method. Optimized conditions increased the specific nitrate reduction rate by 54% and specific nitrite reduction rate by 45%.     

Enhanced stability of hydrogen peroxide in the presence of subsurface solids

The stabilization of hydrogen peroxide was investigated as a basis for enhancing its downgradient transport and contact with contaminants during catalyzed H(2)O(2) propagations (CHP) in situ chemical oxidation (ISCO). Stabilization of hydrogen peroxide was investigated in slurries containing four characterized subsurface solids using phytate, citrate, and malonate as stabilizing agents after screening ten potential stabilizers. The extent of hydrogen peroxide stabilization and the most effective stabilizer were solid-specific; however, phytate was usually the most effective stabilizer, increasing the hydrogen peroxide half-life to as much as 50 times. The degree of stabilization was nearly as effective at 10 mM concentrations as at 250 mM or 1 M concentrations. The effect of stabilization on relative rates of hydroxyl radical activity varied between the subsurface solids, but citrate and malonate generally had a greater positive effect than phytate. The effect of phytate, citrate, and malonate on the relative rates of superoxide generation was minimal to somewhat negative, depending on the solid. The results of this research demonstrate that the stabilizers phytate, citrate, and malonate can significantly increase the half-life of hydrogen peroxide in the presence of subsurface solids during CHP reactions while maintaining a significant portion of the reactive oxygen species activity. Use of these stabilizers in the field will likely improve the delivery of hydrogen peroxide and downgradient treatment during CHP ISCO.     

Transport of Sr2+ and SrEDTA2- in partially-saturated and heterogeneous sediments

Strontium-90 has migrated deep into the unsaturated subsurface beneath leaking storage tanks in the Waste Management Areas (WMA) at the U.S. Department of Energy's (DOE) Hanford Reservation. Faster than expected transport of contaminants in the vadose zone is typically attributed to either physical hydrologic processes such as development of preferential flow pathways, or to geochemical processes such as the formation of stable, anionic complexes with organic chelates, e.g., ethylenediaminetetraacetic acid (EDTA). The goal of this paper is to determine whether hydrological processes in the Hanford sediments can influence the geochemistry of the system and hence control transport of Sr(2+) and SrEDTA(2-). The study used batch isotherms, saturated packed column experiments, and an unsaturated transport experiment in an undisturbed core. Isotherms and repacked column experiments suggested that the SrEDTA(2-) complex was unstable in the presence of Hanford sediments, resulting in dissociation and transport of Sr(2+) as a divalent cation. A decrease in sorption with increasing solid:solution ratio for Sr(2+) and SrEDTA(2-) suggested mineral dissolution resulted in competition for sorption sites and the formation of stable aqueous complexes. This was confirmed by detection of MgEDTA(2-), MnEDTA(2-), PbEDTA(2-), and unidentified Sr and Ca complexes. Displacement of Sr(2+) through a partially-saturated undisturbed core resulted in less retardation and more irreversible sorption than was observed in the saturated repacked columns, and model results suggested a significant reservoir (49%) of immobile water was present during transport through the heterogeneous layered sediments. The undisturbed core was subsequently disassembled along distinct bedding planes and subjected to sequential extractions. Strontium was unequally distributed between carbonates (49%), ion exchange sites (37%), and the oxide (14%) fraction. An inverse relationship between mass wetness and Sr suggested that sandy sediments of low water content constituted the immobile flow regime. Our results suggested that the sequestration of Sr(2+) in partially-saturated, heterogeneous sediments was most likely due to the formation of immobile water in drier regions having low hydraulic conductivities.     

Toxicity of ferric chloride sludge to aquatic organisms

Iron-rich sludge from a drinking water treatment plant (DWTP) was investigated regarding its toxicity to aquatic organisms and physical and chemical composition. In addition, the water quality of the receiving stream near the DWTP was evaluated. Experiments were carried out in August 1998, February 1999 and May 1999. Acute toxicity tests were carried out on a cladoceran (Daphnia similis), a midge (Chironomus xanthus) and a fish (Hyphessobrycon eques). Chronic tests were conducted only on D. similis. Acute sludge toxicity was not detected using any of the aquatic organisms, but chronic effects were observed upon the fecundity of D. similis. Although there were relatively few sample dates, the results suggested that the DWTP sludge had a negative effect on the receiving body as here was increased suspended matter, turbidity, conductivity, chemical oxygen demand (COD) and hardness in the water downstream of the DWTP effluent discharge. The ferric chloride sludge also exhibited high heavy metal concentrations revealing a further potential for pollution and harmful chronic effects on the aquatic biota when the sludge is disposed of without previous treatment.     

Spatial and temporal variations and possible sources of dichlorodiphenyltrichloroethane (DDT) and its metabolites in rivers in Tianjin, China

Water, suspended solid (SS) and sediment samples were collected from nine water courses in Tianjin, China and analyzed for dichlorodiphenyltrichloroethane (DDT) and its metabolites (DDXs, including o,p'-,p,p'-DDT, DDD and DDE). The average DDX concentrations in water, SS and sediment were 59+/-30 ng l(-1), 2690+/-1940 ng g(-1)dry wt. and 340+/-930 ng g(-1)dry wt., respectively. Due to the termination of the extensive agricultural application and industrial manufacture, DDXs in river sediment decreased by one order of magnitude since 1970's and low DDT fractions in these sediments were observed. Still, DDXs in the sediments near the outlets of the major manufacturers remained relatively high attributed to the historic input. DDXs in sediment were also positively correlated with organic matter content. Spatial distributions of DDXs in SS and water was different from that in sediment. For SS, a negative correlation between DDX concentration and SS content indicated a dilution effect in many rivers. Dissolved organic carbon content was the major factor affecting DDX concentrations in water phase. Wastewater discharged from dicofol manufacturers and likely illegal agricultural application were the primary reasons causing high DDT (DDE+DDD) ratios in SS and water.     

The presence of vanadium in groundwater of southeastern extreme the pampean region Argentina Relationship with other chemical elements

Changes in the quality of groundwater resources are related to the presence and concentration of contaminants, especially trace elements such as arsenic, boron, fluoride and vanadium. Vanadium is a rare element naturally abundant, generally found in combination with other elements. Vanadium pentoxide is known to have aneugenic effects. Thus, a study was carried out to assess the presence of vanadium in the groundwater of the southeastern pampean region of Argentina, which constitutes the main water supply for the local population. Statistical and correlational analyses were applied to identify possible interrelationships between vanadium and another chemical elements. Vanadium was found in all groundwater samples. The minimum and maximum vanadium concentrations found were 0.05 mg/l and 2.47 mg/l, respectively. Vanadium is significantly correlated with other trace elements such as arsenic, fluoride and boron. The interrelationship between vanadium and the presence of volcanic glass in sediments is not significant as expected.     

Leaded electronic waste is a possible source material for lead-contaminated jewelry

Highly leaded jewelry, often imported from China, remains widely available in the United States. Leaded electronic waste is exported from the United States to several Asian countries where solder is recovered and circuit boards are stripped of parts in small workshops. To assess whether electronic waste is being recycled into the jewelry, lead, tin and copper content of highly leaded jewelry samples were determined by atomic absorption spectrometry. Sixteen jewelry items previously determined to contain 20-80% lead by weight were analyzed. Samples were digested in nitric acid for analysis of lead and copper, and in aqua regia for analysis of tin. Six samples contained significant amounts of tin, from 20.8% to 29.9% by weight. In addition, copper was a significant minor component of five of these samples (up to 4% by weight). Copper (present at 10-40% by weight in circuit boards) was shown to rapidly move into heated lead-tin solder. The combined lead-tin-copper content of these six items ranges from 93.5% to 100%, suggestive of a solder-based source material. These results are consistent with the hypothesis that recycled circuit board solders are being used to produce some of the heavily leaded imported jewelry sold in the United States. Should this hypothesis be substantiated, it suggests that environmental policies to protect children's health must address both proper recycling of source materials as well as restrictions of the lead content in consumer goods.     

Novel low density granular adsorbents - properties of a composite matrix from zeolitisation of vermiculite

This paper reports the preparation and properties of a new low density granular absorbent material based on a zeolite/vermiculite composite. The composite prepared addresses a number of important issues relating to the use of zeolites in environmental and waste management applications. The material prepared has large particle size due to binderless adhesion of zeolite crystals within the protective lamellar matrix provided by the vermiculite granule. Additionally, the porous nature of new material ensures that it outperforms natural zeolite grains in ion-exchange tests. The material was shown to have a low bulk density (0.75 g cm(-3)) adding the benefit that the majority of grains float on water for over 15 h. The conclusion of the study is that the use of composite matrices enable the preparation of materials which show the physical properties of the host, (e.g., granular and low density), whilst maintaining the powder-like properties (e.g., high ion-exchange and small crystal size) of the active component. The resulting material can be easily handled and separated from aqueous waste streams using either flotation or exploiting its granular nature.