The Influence of pH on Mobility of Heavy Metals from Municipal Solid Waste Incinerator Fly Ash

Incineration has become one of the principal methods for municipal solid waste disposal particularly in all large cities throughout the world. Currently, the municipal solid waste incinerator fly ashes (MSWIF) are disposed of by landfill. The metal speciation of cadmium (Cd), chromium (Cr), copper (Cu), lead (Pb), and zinc (Zn) in MSWIF after been extracted with water at different pH values were examined using a sequential extraction procedure. The extraction sequence was as follows: (1) Exchangeable (NaOAc, pH 8.2), (2) Bound to Carbonates (NaOAc, pH 5.0), (3) Bound to metal oxides (HONH3Cl), (4) Bound to organic matters (HNO3, H2O2), and (5) Residual (HNO3, HCl, H2O2, HF, 1:3:1:3). The heavy metal contents in the extraction solutions were determined by inductively coupled plasma atomic emission spectrometry. The heavy metal concentrations in the different fractions obtained by sequential extraction show distinct distribution trends. The extractable fraction ranges from 25.5 to 88% of the total element content. With the pH of the extractant fall below the neutral and acidic ranges, the concentrations of heavy metals rise substantially due to the released of metals bound to carbonate fraction.     

Biological complexity confounds the separation of point- and non-point sources of human impact on the natural world

Identifying process from pattern is one of the most vexing tasks inenvironmental monitoring. Given information on the distribution of speciesin a pre-defined area, together with comprehensive data on how environmentalconditions in that area have altered through time, is it possible toidentify the factors controlling the species‘ layout? Here, the practicalsignificance of this quandary is demonstrated using a series ofenvironmentally-degraded coastal lagoons in New South Wales. The TuggerahLakes (33°17′S,151°30′E) have over the last 50 yearsexperienced significant changes in species‘ distributions. Seagrasses,macroalgae, phytoplankton, molluscs, prawns and the jellyfish Catostylus mosaicus have altered in spatial pattern. Two human activitieshave been blamed for these perturbations: (1) agricultural clearance ofnative vegetation from the catchment, with associated input of top-soil andnutrients; (2) the commissioning of a coal-fired power station in 1967, withmassive uptake and recirculation of lake water for cooling purposes. In thispaper, spatial changes in macrophyte distributions over the last 50 yearsare reviewed in an attempt to identify the true source(s) of perturbation.The model adopted assumes that the power station is a point source of impactwhile nutrient inputs from the catchment are a diffuse source of impact;changes in species distributions can hypothetically be related back to thesesources according to whether they are localised or widespread. However,after a comprehensive analysis of available macrophyte data derived frominterviews, aerial photography and line transect methodologyies theconclusion is reached that changes in biogeographical pattern around theTuggerah Lakes cannot be attributed to specific anthropogenic pressures atanything beyond the coarsest of levels. This is considered to be the normfor most coastal management situations where natural background variation(’noise‘) and the complexity of linkages between physical, chemical andbiological components confounds the identification of causal relationships.The practical implications of this conclusion are discussed in the contextof litigation and remedial management design. Emphasis is placed on theneed to adopt an adaptive approach to estuarine management, incorporatingexplicit recognition of the limitations of available data, and to developnew techniques for identifying cause-effect relationships.     

Applying mathematical programming to reserve selection

During the last 10–15 years heuristic methods have been developed for problems in optimal reserve selection. Unfortunately, there is no guarantee that heuristics will find optimal solutions. In recognizing this limitation, analysts have formulated reserve selection problems as set covering problems, for which matrix reduction and integer (0/1) programming can be used to find optimal solutions. In this paper we restate the set covering formulation and review solution techniques. A new 0/1 programming model, which is a generalization of the set covering model, is then presented and applied to a hypothetical reserve selection problem. Objectives of minimizing the number of sites selected and maximizing the number of species represented are addressed. Solutions which characterize the tradeoffs between these objectives provide a rich set of information for planners and decision makers. Applications of mathematical programming to related problems in land use planning and forestry are also discussed.     

Optimal and suboptimal control of anaerobic digesters

Anaerobic digester failure due to entry of inhibitors or sudden changes in the feed substrate concentration may be encompassed beneficially by applying optimal control theory. An almost proportional relationship between the dilution rate and the methane production rate leads to a simple suboptimal control law with only minor loss in performance, after the occurrence of the above mentioned events.     

Efficacy of recent state implementation plans for 8-hour ozone

The development of state implementation plans (SIPs) for attainment of criteria pollutant standards is an integral component of air quality management in the United States. However, the content and efficacy of SIPs have rarely been examined systematically. Here, 20 SIPs developed in response to the 1997 8-hr ozone standard are reviewed as case studies of attainment efforts at the state level. Comparison of observed and model predicted ozone concentrations shows the US Environmental Protection Agency (EPA) recommended modeled attainment test to be a somewhat conservative predictor of attainment. Among 12 SIPs for regions that sought attainment by 2009, the test correctly predicted attainment and nonattainment in four and five regions, respectively; in the other three regions, attainment was observed despite predictions of nonattainment. However weight-of-evidence determinations and deviations from the recommended modeled attainment test methodology led five of these SIPs to predict attainment that was not in fact observed by 2009; three of those regions achieved attainment in 2010. Ozone and NO2 concentrations declined across much of the United States during the period covered by the SIPs, with rates of improvement strongly correlated with the initial pollution levels and hence greatest in nonattainment regions. However at monitors with mid-range levels of ozone initially, rates of reduction were largely independent of the initial attainment status of the region. This is consistent with thefact that apart from California, the majority of ozone precursor reductions documented by SIPs resulted from federal measures rather than from state or local controls specific to the nonattainment regions.     

Occurrence of alternative flame retardants in indoor dust from New Zealand: indoor sources and human exposure assessment

Due to worldwide restrictions on polybrominated diphenyl ethers (PBDEs), the demand for alternative flame retardants (AFRs), such as organophosphate flame retardants (OPFRs), novel brominated FRs (NBFRs) and hexabromocyclododecanes (HBCDs), has recently increased. Little is known about human exposure to NBFRs and OPFRs and that their levels in dust have been scarcely evaluated worldwide. To increase the knowledge regarding these chemicals, we measured concentrations of five major NBFRs, ten OPFRs and three HBCD isomers in indoor dust from New Zealand homes. Dust samples were taken from living room floors (n=34) and from mattresses of the same houses (n=16). Concentrations (ngg(-1)) of NBFRs were: 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) (<2-175), decabromodiphenyl ethane (DBDPE) (<5-1430), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB) (<2-2285) and bis(2-ethylhexyl)-3,4,5,6-tetrabromophthalate (TBPH) (<2-640). For OPFRs, concentrations (ngg(-1)) ranged between: tri-ethyl-phosphate (TEP) (<10-235), tri-n-butyl-phosphate (TnBP) (<20-7545), tris-(2-chloroethyl)-phosphate (TCEP) (<20-7605), tris-(1-chloro-2-propyl) phosphate (TCPP) (20-7615), tri-(2-butoxyethyl)-phosphate (TBEP) (50-27325), tris-(2,3-dichloropropyl)-phosphate (TDCPP) (20-16560), tri-phenyl-phosphate (TPhP) (20-35190), and tri-cresyl-phosphate (TCP) (<50-3760). HBCD concentrations fell in the range <2-4100ngg(-1). BTBPE, DBDPE, TBPH, TBEP, and TnBP showed significant positive correlation (p<0.05) between their concentrations in mattresses and the corresponding floor dust (n=16). These data were used to derive a range of plausible exposure scenarios. Although the estimated exposure is well below the corresponding reference doses (RfDs), caution is needed given the likely future increase in use of these FRs and the currently unknown contribution to human exposure by other pathways such as inhalation and diet.     

Acute toxicity tests with Daphnia magna, Americamysis bahia, Chironomus riparius and Gammarus pulex and implications of new EU requirements for the aquatic effect assessment of insecticides

Threshold concentrations for treatment related effects of 31 insecticides, as derived from aquatic micro-/mesocosm tests, were used to calibrate the predictive value of the European Tier-1 acute effect assessment on basis of laboratory toxicity tests with Daphnia magna, Chironomus spp., Americamysis bahia and Gammarus pulex. The acute Tier-1 effect assessment on basis of Daphnia (EC(50)/100) overall was protective for organophosphates, carbamates and most pyrethroids but not for neonicotinoids and the majority of insect growth regulators (IGRs) in the database. By including the 28-day water-spiked Chironomus riparius test, the effect assessment improves but selecting the lowest value on basis of the 48-h Daphnia test (EC50/100) and the 28-day Chironomus test (NOEC/10) is not fully protective for 4 out of 23 insecticide cases. An assessment on basis of G. pulex (EC(50)/100) is sufficiently protective for 15 out of 19 insecticide cases. The Tier-1 procedure on basis of acute toxicity data (EC(50)/100) for the combination of Daphnia and A. bahia and/or Chironomus (new EU dossier requirements currently under discussion) overall is protective to pulsed insecticide exposures in micro-/mesocosms. For IGRs that affect moulting, the effect assessment on basis of the 48-h Chironomus test (EC(50)/100) may not always be protective enough to replace that of the water-spiked 28-day C. riparius test (NOEC/10) because of latency of effects.     

Impact of injection system design on ISCO performance with permanganate--mathematical modeling results

In situ chemical oxidation (ISCO) using permanganate (MnO(4)(-)) can be a very effective technique for remediation of soil and groundwater contaminated with chlorinated solvents. However, many ISCO projects are less effective than desired because of poor delivery of the chemical reagents to the treatment zone. In this work, the numerical model RT3D was modified and applied to evaluate the effect of aquifer characteristics and injection system design on contact and treatment efficiency. MnO(4)(-) consumption was simulated assuming the natural oxidant demand (NOD) is composed of a fraction that reacts instantaneously and a fraction that slowly reacts following a 2nd order relationship where NOD consumption rate increases with increasing MnO(4)(-) concentration. MnO(4)(-) consumption by the contaminant was simulated as an instantaneous reaction. Simulation results indicate that the mass of permanganate and volume of water injected has the greatest impact on aquifer contact efficiency and contaminant treatment efficiency. Several small injection events are not expected to increase contact efficiency compared to a single large injection event, and can increase the amount of un-reacted MnO(4)(-) released down-gradient. High groundwater flow velocities can increase the fraction of aquifer contacted. Initial contaminant concentration and contaminant retardation factor have only a minor impact on volume contact efficiency. Aquifer heterogeneity can have both positive and negative impacts on remediation system performance, depending on the injection system design.     

Changes in the pore network structure of Hanford sediment after reaction with caustic tank wastes

At the former nuclear weapon production site in Hanford, WA, caustic radioactive tank waste leaks into subsurface sediments and causes dissolution of quartz and aluminosilicate minerals, and precipitation of sodalite and cancrinite. This work examines changes in pore structure due to these reactions in a previously-conducted column experiment. The column was sectioned and 2D images of the pore space were generated using backscattered electron microscopy and energy dispersive X-ray spectroscopy. A pre-precipitation scenario was created by digitally removing mineral matter identified as secondary precipitates. Porosity, determined by segmenting the images to distinguish pore space from mineral matter, was up to 0.11 less after reaction. Erosion-dilation analysis was used to compute pore and throat size distributions. Images with precipitation had more small and fewer large pores. Precipitation decreased throat sizes and the abundance of large throats. These findings agree with previous findings based on 3D X-ray CMT imaging, observing decreased porosity, clogging of small throats, and little change in large throats. However, 2D imaging found an increase in small pores, mainly in intragranular regions or below the resolution of the 3D images. Also, an increase in large pores observed via 3D imaging was not observed in the 2D analysis. Changes in flow conducting throats that are the key permeability-controlling features were observed in both methods.