Experimental study and modelling of lead solubility as a function of pH in mixtures of ground waters and cement waters

The purpose of this study was the simulation of lead solubility equilibria in mixtures of concrete lixiviation waters and ground waters in order to obtain the data necessary for the modelling of lead behaviour. The lixiviation water was impossible to obtain in sufficient quantity by compression of concrete specimens and was replaced by cement water prepared by mixing a CLC or CPA cement suspension in distilled water under argon. Three lead salts, PbCl2, PbSO4 and PbCO3, were studied; they correspond to the anions found most frequently in the ground waters. The experimental curves of lead solubility were determined, at 20 degrees C, from pH 5 to 13, for various systems: cement water/lead salt/ground water. The modelling of 10 systems was carried out by the PHREEQC code from the solution compositions (ground water and cement water mixtures) and the thermodynamic constants obtained from the MINTEQ data base. The chemical models included the nature of the species in solution and the solid phases in equilibrium together with the corresponding values for the logarithms of the formation constants or solubility products. These models were validated by comparing the experimental pH and solubilised lead concentration values with the values calculated using the PHREEQC code.     

Influence of sediment redox conditions on release/solubility of metals and nutrients in a Louisiana Mississippi River deltaic plain freshwater lake

The influence of sediment redox conditions on solubility of selected metals and nutrients in sediment from a coastal Louisiana freshwater lake (Lake Cataouatche) receiving diverted Mississippi River water was quantified. Sediment redox was cycled step wise in 50 mV increments between oxidized (-200 to +500 mV) and reduced (+500 to -200 mV) conditions. Changes in sediment oxidation/reduction status and pH influenced solubility of both metals and nutrients. When redox potential (Eh) was increased from -200 to +500 mV, sediment pH decreased from 7.1 to 5.7. When the sediment Eh decreased from +500 to -200 mV, pH increased from 5.7 to 7.1. The increase in sediment acidity upon oxidation resulted in the release of the Pb, Ca, Mg, Al, and Zn into solution. The solution concentration of these elements was inversely proportional to Eh (P相似文献   

Metal speciation in sulphidic sediments: a new method based on oxidation kinetics modelling in the presence of EDTA

The solid phase partitioning of metals (Zn, Cu and Pb) was determined in four anoxic, metal polluted sediments by investigating at pH 8 the 1 day oxidation kinetics of the metal sulphide phases present in the sediments in a background solution containing excess EDTA. A mathematical model consisting of a combination of two pseudo-first order reactions was used to fit the metal release data as a function of oxidation time. The model permitted to fractionate the trace metals in a 'quickly-oxidizable' and a 'slowly-oxidizable' fraction, which could be assigned to two different trace metal pools, respectively (1) FeS minerals (e.g. amorphous FeS, mackinawite) and (2) discrete trace metal sulphide phases. The sum of the fractions associated with these sulphide pools was taken as an approximation for the sulphide-associated fraction of the trace metals and coincided (for the case of Zn and Pb) with the sulphide-associated fraction derived from the analysis of acid volatile sulphide (AVS) and simultaneously extracted metals (SEM). Oxidation kinetics modelling allowed also determining the sulphide-associated fraction of a broad range of trace metals (as demonstrated for Cu) more accurately than the AVS/SEM method, which suffers from non-efficient extraction of a number of trace metal sulphides. A correction was made for the determination of the sulphide-associated fraction by subtracting the trace metal fraction dissolved after 1 day under anoxic conditions in the background EDTA solution. The combination of (1) one day oxidation kinetics modelling and (2) correction for the 1 day anoxic EDTA-soluble fraction is a suitable method to determine accurately the true sulphide speciation of trace metals in anoxic sediments.     

Simultaneous release of sulfide with Fe, Mn, Ni and Zn in marine harbour sediment measured using a combined metal/sulfide DGT probe

The technique of DGT (Diffusive Gradients in Thin Films) was further developed to allow simultaneous measurement of sulfide and trace metals at the same location in sediment. The new combined DGT probe consisted of a layer of gel impregnated with AgI, overlain by (1) a layer of gel containing Chelex, (2) a layer of gel and (3) a filter membrane. Diffusion of sulfide was controlled by layers (1) to (3), while diffusion of metals was controlled by layers (2) and (3). The Chelex gel trapped metals that were measured after elution with acid. The AgI gel trapped sulfide through the formation of Ag2S. This was then measured densitometrically as the colour changed from pale yellow to grey. Experiments demonstrated that concentrations of metal or sulfide measured by the combined device were no different to the concentrations measured by more conventional devices. The presence of Chelex in the gel did not impede the diffusion of sulfide. Deployment of a combined probe in marine sediment revealed simultaneous remobilisation of metals and sulfide at the same location. Solubility calculations indicated that some precipitation of amorphous FeS was probably occurring at the maxima in sulfide concentrations. There was general undersaturation with respect to NiS, but ZnS was supersaturated at all locations. There appeared to be localised active zones of organic matter decomposition, where reduction of manganese oxides, iron oxides and sulfate occurred simultaneously. Mass balance calculations indicated that Ni could not be supplied by release from decomposing organic matter. Manganese oxides were the most likely source, but supply from reductive dissolution of iron oxides could not be entirely discounted. Supply from either Fe or Mn oxides could account for the Zn maxima. Application of the newly developed combined probe provides new information that helps understanding of the complex nature of trace metal and sulfur chemistry in sediments.     

Suspended particle destabilization in retained urban stormwater as a function of coagulant dosage and redox conditions

Source area runoff entrains a hetero-disperse particle size distribution (PSD). When retained for clarification, larger sediment and settleable particles are mainly influenced by gravitational forces, while the suspended particles, in particular the clay-size particles, are subject to coagulation phenomena. Such phenomena occur in untreated runoff as well as runoff treated with a coagulant, albeit to differing rates and extents. Runoff PSDs and water chemistry indices including zeta potential (xi) are potentially modified during inter-event stormwater retention in best management practices (BMPs). This study examined xi of clay-size particles (<2 microm) in retained runoff, captured from an instrumented watershed, subject to batch coagulation and variable redox conditions. Separate parallel tests were also conducted with wastewater. Significant turbidity, particle mass (measured as total suspended solids (TSS)) and volume concentration (as total volume concentration (TVC)) reduction generated by alum and ferric chloride consistently occurred at a xi in the range of -15 to about -10 mV. Alum addition produced a charge reversal at dosing above 60 mg/L (18 x 10(-5)M) while ferric chloride did not reverse charge. With respect to turbidity and TSS reductions, alum outperformed ferric chloride, without the need for pH control. While xi illustrated no clear trend during aerobic retention, anoxic retention resulted in a trend for xi approaching the isoelectric point. The decrease in negative xi towards the isoelectric point appears to be a result of the coupled pH depression under reductive conditions and an increase in conductivity. Results have significant implications for BMPs that retain runoff between events.     

New approach to optimize operational conditions for the biological treatment of a high-strength thiocyanate and ammonium waste: pH as key factor

Biological treatment of coke and steel-processing wastewaters has to satisfy both industrial economic needs and environmental protection regulations. Nevertheless, as some of the pollutants contained in these waters or produced during the treatment are highly toxic, an effective and safe treatment has proved to be difficult to obtain. This paper reports the study of a biological method for the treatment of wastewaters containing free cyanide, thiocyanate and ammonium (NH4). Laboratory-scale activated-sludge reactors were fed with a synthetic solution reproducing a steel-processing industrial wastewater and inoculated with the same industrial bacterial seeding used on-site (Ecosynergie Inc.). The results demonstrated that free cyanide and thiocyanate were efficiently degraded. Nevertheless, thiocyanate degradation and nitrification processes were actually inhibited by the free ammonia form (NH3) in place of the ionized NH4 form (NH4+) currently dosed and often unproperly named "ammonia" [IUPAC, 1997. In: McNaught, A.D., Wilkinson, A. (compilers). Compendium of Chemical Terminology. Royal Society of Chemistry, Cambridge, UK]. Optimum degradation rates were obtained for very narrow ranges of ammonia nitrogen (NH3-N) concentrations. This result can be explained by the role of pH, which mainly controls the NH3/NH4 equilibrium. Pollutants and NH3 concentrations influenced degradation rates of main pollutants. This influence was determined and expressed through elementary equations. Although the Michaelis-Menten equation could have been used to describe thiocyanate degradation, a Haldane-inhibition model was used to satisfactorily describe cyanide degradation. On the other hand, a slightly modified Haldane model was applied to describe both NH4 oxidation using NH3-N as substrate and thiocyanate degradation using NH3-N as inhibitor. These findings emphasize the role of pH on degradation rates and allow one to optimize operational conditions in the biological treatment of coke and steel industrial wastewaters.     

The highway as a source of water pollution: An appraisal with the heavy metal lead

Factors influencing the impact of highway lead on the quality of water resources are discussed, and the available information on each factor critically evaluated. Hence, the sources of lead input to the highway environment are described and the subsequent airborne and waterborne dispersal to the receiving waters discussed in detail. It appears that the impact on surface waters is confined to the lead contained in surface runoff, as the lead dispersed to roadside soils is effectively immobilized in the top 10 cm of soil. The concentration of lead in highway runoff can reach levels far in excess of those normally encountered in surface waters. However, when evaluating the impact on the receiving waters, the importance of considering both the lead mass discharge from the highway and the subsequent dilution by the receiving water is stressed. Finally, the present inadequate understanding of the physiochemical forms of lead in polluted and natural waters is highlighted.     

Elimination and fate of selected micro-organic pollutants in a full-scale anaerobic/anoxic/aerobic process combined with membrane bioreactor for municipal wastewater reclamation

The occurrence and elimination of 19 micro-organic pollutants including endocrine disrupting chemicals (EDCs) and pharmaceuticals and personal care products (PPCPs) in a full-scale anaerobic/anoxic/aerobic-membrane bioreactor process was investigated. The investigated process achieved over 70% removal of the target EDCs and 50%–100% removal of most of the PPCPs, with influent concentration ranging from ng/L to μg/L. Three PPCPs, carbamazepine, diclofenac and sulpiride were not well removed, with the removal efficiency below 20%. A rough mass balance suggests that the targets were eliminated through sludge-adsorption and/or biodegradation, the former of which was particularly significant for the removal of hydrophobic compounds. The two-phase fate model was employed to describe the kinetics of sludge-adsorption and biodegradation. It was found that the fast sludge adsorption (indicated by mass-transfer rates greater than 10 for most compounds) is responsible for the rapid decline of the aqueous concentration of the targets in the first compartment of the treatment process (i.e. in the anaerobic tank). In contrast, the slow biodegradation proved to be the rate-determining step for the entire degradation process, and the rates are generally positively related to the dissolved oxygen level. On the other hand, this study showed that the removal rates of most targets can reach a quasi-plateau in 5 h under aerobic conditions, indicating that hydraulic retention time of ca. 5 h in aerobic tanks should be sufficient for the elimination of most targets.     

Stepwise effects of the BCR sequential chemical extraction procedure on dissolution and metal release from common ferromagnesian clay minerals: a combined solution chemistry and X-ray powder diffraction study

Sequential extraction procedures (SEPs) are commonly used to determine speciation of trace metals in soils and sediments. However, the non-selectivity of reagents for targeted phases has remained a lingering concern. Furthermore, potentially reactive phases such as phyllosilicate clay minerals often contain trace metals in structural sites, and their reactivity has not been quantified. Accordingly, the objective of this study is to analyze the behavior of trace metal-bearing clay minerals exposed to the revised BCR 3-step plus aqua regia SEP. Mineral quantification based on stoichiometric analysis and quantitative powder X-ray diffraction (XRD) documents progressive dissolution of chlorite (CCa-2 ripidolite) and two varieties of smectite (SapCa-2 saponite and SWa-1 nontronite) during steps 1-3 of the BCR procedure. In total, 8 (± 1) % of ripidolite, 19 (± 1) % of saponite, and 19 (± 3) % of nontronite (% mineral mass) dissolved during extractions assumed by many researchers to release trace metals from exchange sites, carbonates, hydroxides, sulfides and organic matter. For all three reference clays, release of Ni into solution is correlated with clay dissolution. Hydrolysis of relatively weak Mg-O bonds (362 kJ/mol) during all stages, reduction of Fe(III) during hydroxylamine hydrochloride extraction and oxidation of Fe(II) during hydrogen peroxide extraction are the main reasons for clay mineral dissolution. These findings underscore the need for precise mineral quantification when using SEPs to understand the origin/partitioning of trace metals with solid phases.     

Effects of pH and phosphate on metal distribution with emphasis on As speciation and mobilization in soils from a lead smelting site

Arsenic in soils from the Asarco lead smelter in East Helena, Montana was characterized by X-ray absorption spectroscopy (XAS). Arsenic oxidation state and geochemical speciation were analyzed as a function of depth (two sampling sites) and surface distribution. These results were compared with intensive desorption/dissolution experiments performed in a pH stat reactor for samples from the site with the highest degree of As heterogeneity. The objectives of the study were to investigate the solid-phase geochemical As speciation, assess the speciation of As in solutions equilibrated with the solids under controlled pH (pH=4 or 6) and Eh (using hydrogen or air) environments, observe the effects of phosphate on the release of As into solution, and examine the effects of phosphate on metal mobility in the systems. Arsenic was predominantly found in the As(V) valence state, though there was evidence that As(III) and As(0) were present also. The dominant geochemical phase was scorodite (FeAsO4.2H2O). The pH was controlled in the pH stat experiments by the addition of equinormal solutions of monoprotic (HNO3), diprotic (H2SO4), or triprotic (H3PO4) acids. For many of the divalent metal cations, solution concentrations greatly decreased in the presence of phosphate. Solutions were also analyzed for anions. Evidence exists for sulfate release into solution. More As was released into solution at lower pH. A slight increase in solution arsenate occurs with the addition of phosphate, but the risk posed from the increased desorption/dissolution of As must be weighed against the decrease in solution concentrations of many metals especially Pb. If tailings from this site underwent acidification (e.g., acid mine drainage), in situ sequestration of metals by phosphate could be combined with placement of subsurface permeable reactive barriers for capture of As to reduce the risk associated with arsenic and trace metal mobilization. Results from this study could be used in risk management plans for sites similar to the Pb smelter site examined here.     

Numerical modeling of an umbrella arch as a pre-support system in difficult geological conditions: a case study

In order to prevent the collapse of ceilings and walls of large tunnels, especially in difficult geological conditions, either a sequential excavation method (SEM) or ground reinforcing method, or a combination of both, can be utilized. The first part of the adit tunnel in northwestern Iran is being drilled in alluvium material with very weak geotechnical parameters. Despite applying an SEM in constructing this tunnel, analyzing the numerical modeling done using FLAC3D, as well as observations during drilling, indicate tunnel instability. To increase operational safety and to prevent collapse, a pre-support system was designed and implemented. The results of the numerical modeling accompanied by monitoring during operation, as well as the results of instrumentation, indicate the efficacy of this method for preventing collapse in alluvium material along the tunnel route. Modeling the behavior of the umbrella arch shows that the location of the maximum compressive force will change with a change in the tunnel arc location. Moreover, displacement, force and moment exerted on the pipes will change during drilling steps according to a certain pattern.     

Effect of pH on the concentrations of lead and trace contaminants in drinking water: a combined batch, pipe loop and sentinel home study

High lead levels in drinking water are still a concern for households serviced by lead pipes in many parts of North America and Europe. This contribution focuses on the effect of pH on lead concentrations in drinking water delivered through lead pipes. Though this has been addressed in the past, we have conducted a combined batch, pipe loop and sentinel study aiming at filling some of the gaps present in the literature. Exhumed lead pipes and water quality data from the City of London’s water distribution system were used in this study. As expected, the lead solubility of corrosion scale generally decreased as pH increased; whereas dissolution of other accumulated metals present in the corrosion scale followed a variety of trends. Moreover, dissolved arsenic and aluminum concentrations showed a strong correlation, indicating that the aluminosilicate phase present in the scale accumulates arsenic. A significant fraction of the total lead concentration in water was traced to particulate lead. Our results indicate that particulate lead is the primary contributor to total lead concentration in flowing systems, whereas particulate lead contribution to total lead concentrations for stagnated systems becomes significant only at high water pH values.     

Case study on the use of a combined system as an intermediate solution in Brazil: cost estimate

As a developing country, Brazil has to deal with a lack of basic sanitation. One of the major challenges is the treatment of wastewater. While 94% of Brazilian municipalities have stormwater systems, only 55% are connected to a wastewater system. To help improve the current situation, this study estimates the costs for implementing an intermediate solution, which is designed to ease the transition towards a separate wastewater treatment system. This solution utilizes a combined sewer system approach in areas where stormwater systems have already been implemented. A case study was carried out assessing two possible alternatives for a wastewater treatment system with data from the city of Joinville. Both alternatives are separate systems but one has a combined system as an intermediate solution. The results show that the alternative with an intermediate combined system will reduce the short‐term financial burden on governments in comparison to the separate sewer system approach.     

Determination of caffeine as a tracer of sewage effluent in natural waters by on-line solid-phase extraction and liquid chromatography with diode-array detection

A new liquid chromatographic (LC) method with automated on-line solid phase extraction was developed to determine caffeine at sub-microgram per litre concentrations in waters. The filtered sample was pre-concentrated in a pre-column, which was backwashed with acidic water at pH of 2.70. The concentrated caffeine was separated using a C18 column with a gradient of water-acetonitrile and detected by diode array detection (DAD) at 210 nm. Four different pre-columns: C18, PRP-1, PLRP-s and Env were evaluated for the on-line solid phase extraction of caffeine. The PLRP-s pre-column allowed the enrichment of up to 100 mL of environmental water sample with highest recovery. The procedure was validated by recovery experiments in water spiked at 0.5 1.0 and 4.0 microg/L. Average recoveries were between 92.1 +/- 5.2% and 97.8 +/- 2.6%. Detection limits as low as 0.1 microg/L from 50 ml of sample were achieved. The proposed method has the advantages of higher reliability and sensitivity, simpler sample preparation and shorter analysis time in comparison with off-line solid-phase extraction. The utility of the method was demonstrated at two field sites: Bolivar and Halls Head (Australia). At Bolivar, the treatment process included 6-week lagoon storage which is believed to have attenuated caffeine, and thus limited its use as an environmental tracer of reclaimed water. At the Halls Head site, where the storage period is shorter, caffeine was detected in both the treated sewage effluent and in groundwater near ponds where the reclaimed water is at similar concentrations. These results suggest that the environmental conditions under which caffeine is conservative require better definition.     

The chelation of cadmium with NTA in sea water as a model for the typical behaviour of trace heavy metal chelates in natural waters

As a typical example for chelates of heavy metal traces in sea water, the chelation of the toxic metal cadmium with the potential pollutant nitrilotriacetic acid (NTA) as ligand at the low Cd(II) concentration of 10^?7 M and less, realistic for polluted waters, has been studied by differential pulse polarography. Detailed investigations with model solutions of singular macro-salt-components of sea water, with artificial and with natural sea water from the Adriatic have revealed the specific influences of the significant relevant macro-components of sea water on the stability of heavy metal chelates in the sea in principle, and on the chelation of Cd(II) with NTA in particular. From the methodological aspect the approach described in generally applicable to the study of other chelates with heavy metal traces in sea water and inland waters. The distribution of Cd(II) over various chemical species to be expected in sea water in the presence of given amounts of NTA has been evaluated.     

Exploration of remediation of acid rock drainage with clinoptilolite as sorbent in a slurry bubble column for both heavy metal capture and regeneration

Preliminary work was carried out to explore a novel process for high-efficiency high-capacity remediation of acid rock drainage. Zn and other metal ions were adsorbed and desorbed in a laboratory Plexiglas slurry bubble column with natural clinoptilolite particles as sorbent. The results indicate that both adsorption and desorption in this medium have considerable advantages over those in the packed beds and rotating columns, leading to faster batch adsorption and desorption, as well as greater uptake of zinc. The adsorption order of clinoptilolite particles to different metal ions appeared to be Fe>Al>Cu>Zn>Mg>Mn on the basis of normalized concentrations. Smaller particles had significantly higher capacity and rates of the adsorption than larger particles for the same operating conditions.     

Mercury bioacumulation in four tissues of Podocnemis erythrocephala (Podocnemididae: Testudines) as a function of water parameters

A number of environmental factors influence the dynamics of Hg in aquatic ecosystems, yet few studies have examined these factors for turtles, especially from South America. Red-headed river turtle (Podocnemis erythrocephala) is easy to capture in the black waters of Rio Negro, making it the turtle species that is consumed most often by people of the region. In this study, environmental factors and turtle size were investigated to determine their influence on the Hg concentration in blood, muscle, liver and carapace of the red-headed river turtle. Factors investigated included turtle length, pH, dissolved organic carbon and availability of potential methylation sites (floodplain forests and hydromorphic soils). The study was conducted in the Rio Negro basin, where we collected water and turtle blood, muscle, liver and carapace samples from 12 tributaries for chemical analysis. Through radar imagery and existing soil maps with GIS, the percentage of alluvial floodplains and hydromorphic soils (potential methylation sites) was estimated for each drainage basin at sampling points. The mean Hg concentration in blood of P. erythrocephala was 1.64 ng g^− 1 (SD = 1.36), muscle 33 ng g^− 1 (SD = 11), liver 470 ng g^− 1 (SD = 313) and carapace 68 ng g^− 1 (SD = 32). Sex or length did not influence the Hg concentration in P. erythrocephala blood, muscle and liver, but Hg increased in carapace tissue when length size increased (ANCOVA p = 0.007). In the multiple regression analysis, none of the environmental factors studied had a significant relation with blood, muscle, liver and carapace. P. erythrocephala moves among habitats and in the open and interconnected aquatic systems of the Amazon basin, characterized by high levels of limnological variability, a good bioindicator of Hg concentration needs to be relatively sedentary to represent a specific habitat. However, the levels of Hg in liver were sufficient to pose a potential risk to humans that consume them, suggesting the usefulness of P. erythrocephala as a bioindicator.     

Behaviour of uranium in iron-bearing permeable reactive barriers: investigation with 237U as a radioindicator

This study was undertaken to investigate the long-term performance of elemental iron as reactive material for the removal of uranium in passive groundwater remediation systems. By using 237U as a radioindicator it was possible to track the movement of the contamination front through a test column without taking samples or dismantling the apparatus. The stoichiometric ratio between uranium and iron was found to be 1:(1390+/-62). The reaction between iron and uranium is of pseudo first-order kinetics and the rate constant was measured to be (1.1+/-0.09) x 10(-3) s(-1). These data enable the calculation of ideal lifetime for permeable reactive barriers (PRB) using iron for uranium removal neglecting hydrological factors that may impair the function of PRBs.     

Universal mitochondrial PCR combined with species-specific dot-blot assay as a source-tracking method of human, bovine, chicken, ovine, and porcine in fecal-contaminated surface water

Mitochondrial (mt) DNA has the potential to be used as an animal-specific genetic marker for source-tracking of fecal contamination in surface waters and groundwaters. In this report, we describe the development of a method to detect in a single assay human, bovine, ovine, porcine and chicken mitochondrial (mt) DNA in water. Consensus nucleic sequences were found between human, bovine, porcine, ovine and chicken mtDNA to design three sets of PCR universal primers. Upon polymerase chain reaction (PCR) with a digoxigenin-labeled nucleotide and the universal primers, species determination was carried out by dot-blotting membranes containing specific oligonucleotides for these five animals. Our method was carried out with three river samples and three wastewater samples, and the results were compared with those obtained by multiple nested PCR with specific primers for these five species. Our results showed that the dot-blot assays were as specific and sensitive as the nested-PCR approach. The proposed method has the advantage that it requires the use of only one PCR per sample and very little amounts of DNA. Finally, it is an alternative to multiplex PCR approach which is less sensitive, and shows the way for the development of DNA arrays for source-tracking of many more animal species in fecal-contaminated water.