Coagulation behavior of aluminum salts in eutrophic water: significance of Al13 species and pH control

The coagulation behavior of aluminum salts in a eutrophic source water was investigated from the viewpoint of Al(III) hydrolysis species transformation. Particular emphasis was paid to the coagulation effect of Al13 species on removing particles and organic matter. The coagulation behavior of Al coagulants with different basicities was examined through jar tests and hydrolyzed Al(III) speciation distribution characterization in the coagulation process. The results showed that the coagulation efficiency of Al coagulants positively correlated with the content of Al13 in the coagulation process ratherthan in the initial coagulants. Aluminum chloride (AICl3) was more effective than polyaluminum chloride (PACI) in removing turbidity and dissolved organic matter in eutrophic water because AlCl3 could not only generate Al13 species but also function as a pH control agent in the coagulation process. The solidstate 27Al NMR spectra revealed that the precipitates formed from AlCl3 and PACl were significantly different and proved that the preformed Al13 polymer was more stable than the in situ formed one during the coagulation process. Through regulating Al speciation, pH control could improve the coagulation process especially in DOC removal, and AlCl3 benefited most from pH control.     

Characterization of disinfection byproduct precursors based on hydrophobicity and molecular size

Natural organic matter (NOM) from five water sources was fractionated using XAD resins and ultrafiltration membranes into different groups based on hydrophobicity and molecular weight (MW), respectively. The disinfection byproduct formation from each fraction during chlorination and chloramination was studied. In tests using chlorination, hydrophobic and high MW (e.g., >0.5 kDa) precursors produced more unknown total organic halogen (UTOX) than corresponding hydrophilic and low MW (e.g., <0.5 kDa) precursors. Trihaloacetic acid (THAA) precursors were more hydrophobic than trihalomethane (THM) precursors. The formation of THM and THAA was similar among different fractions for a water with low humic content. Hydrophilic and low MW (<0.5 kDa) NOM fractions gave the highest dihaloacetic acid (DHAA) yields. No significant difference was found for DHAA formation among different NOM fractions during chloramination. Increasing pH from 6 to 9 led to lower TOX formation for hydrophobic and high MW NOM fractions but had little impact on TOX yields from hydrophilic and low MW fractions. Bromine and iodine were more reactive with hydrophilic and low MW precursors as measured by THM or HAA formation than their corresponding hydrophobic and high MW precursors. However, hydrophobic and high MW precursors produced more UTOX when reacting with bromine and iodine.     

Disinfection byproduct relationships and speciation in chlorinated nanofiltered waters

The formation and speciation of disinfection byproducts (DBPs) resulting from chlorination of nanofilter permeates obtained from various source water locations and membrane types are examined. Specific ultraviolet absorbance and bromide utilization are shown to decrease following nanofiltration. Both dissolved organic carbon (DOC) concentration and ultraviolet absorbance at 254 nm were found to correlate strongly with trihalomethane (THM), haloacetic acid (HAA), and total organic halide (TOX) concentrations in chlorinated nanofilter permeates, suggesting that they can be employed as surrogates for DBPs in nanofiltered waters. Because smooth curves were obtained for individual THM and HAA species as well as bromine and chlorine incorporation into THMs and HAAs as a function of Br-/DOC molar ratio, it is likely that mole fractions of these DBPs are more strongly influenced by chlorination conditions, Br-, and DOC concentrations than NOM source and membrane type. Mole fractions of mono-, di-, and trihalogenated HAAs were found to be independent of Br-/DOC. Even at a very low Br-/DOC of 2.9microM/mM, the mixed bromochloro- and tribromoacetic acids constituted 20% of total HAAs on a molar basis. This increased to approximately 50% as Br-/DOC increased to approximately 25microM/mM or more, proving that a large fraction of HAAs may not be covered under existing federal regulations. Total THM and HAA9 concentrations decreased in permeate waters with increasing Br-/DOC suggesting that nanofilter permeates are limited with respect to DBP precursors.     

Relative importance of charge neutralization and precipitation on coagulation of Kaolin with PACI: effect of sulfate ion

The effect of the sulfate ion on coagulation with polyaluminum chloride (PACl) was investigated by using an optical monitoring technique together with the conventional jar test procedure and electrophoretic mobility (EM) measurements. The effect of the SO4(2-)/Al ratio, dosage, and pH were examined in detail. The experimental results show that sulfate has a significantly different effect on PACl coagulation as a result of preformed hydrolysis products, where charge neutralization and precipitation play different parts in the coagulation process. The increased rate of coagulation with increasing SO4(2-)/Al ratio can be partially explained by charge neutralization effects, through increased adsorption and complexation of sulfate, thus giving increased particle collision efficiency. Different PACl samples were prepared with different values of B ([OH]/[Al]). For B = 0 (i.e., AlCl3) with mainly monomers, hydroxide precipitation tends to be accelerated in the presence of sulfate, giving significant turbidity removal. The high charge neutralization ability remains for samples with B = 1.5 and 2.0, with large proportions of preformed oligomers and polymers. Sulfate promotes aggregation of hydrolyzed species for B= 2.5, causing significantly improved coagulation efficiency through an electrostatic patch effect. The results illustrate further that particle charge plays a less important role in coagulation after reaching a certain value, while precipitate formation improves coagulation significantly.     

Impact of simulated solar irradiation on disinfection byproduct precursors

The Sacramento-San Joaquin Delta is the major drinking water source for 23 million California residents. Consequently, many studies have examined disinfection byproduct (DBP) formation in relation to Delta dissolved organic carbon (DOC) concentration. However, DOC characteristics within the Delta are not the same as those entering downstream water treatment facilities. As water is transferred to Southern California through the California Aqueduct, a 714.5 km-open channel, it is exposed to sunlight, potentially altering DBP precursors. We collected water from three sites within the Delta and one nearthe California Aqueduct, representing different DOC sources, and irradiated them in a solar simulator at a dose equivalent to that received during four days conveyance in the aqueduct. Photolytic changes in DOC were assessed by measuring CO2 and organic acid production, fluorescence, and ultraviolet absorbance over time. Trihalomethane (THM) and haloacetic acid (HAA) formation potentials, as well as the distribution of hydrophobic, transphilic, and hydrophilic acid fractions were determined at exposures equivalent to one and four days. Solar irradiation significantly decreased ultraviolet absorbance and fluorescence intensity, produced organic acids, and increased the hydrophilic fraction of waters. These changes in DOC caused a shift in bromine incorporation among the THM and HAA species. Our results are the first to demonstrate the importance of sunlight in altering DOC with respect to DBP formation.     

Haloacetic acid and trihalomethane formation from the chlorination and bromination of aliphatic beta-dicarbonyl acid model compounds

While it is known that resorcinol- and phenol-type aromatic structures within natural organic matter (NOM) react during drinking water chlorination to form trihalomethanes (THMs), limited studies have examined aliphatic-type structures as THM and haloacetic acid (HAA) precursors. A suite of aliphatic acid model compounds were chlorinated and brominated separately in controlled laboratory-scale batch experiments. Four and two beta-dicarbonyl acid compounds were found to be important precursors for the formation of THMs (chloroform and bromoform (71-91% mol/mol)), and dihaloacetic acids (DXAAs) (dichloroacetic acid and dibromoacetic acid (5-68% mol/mol)), respectively, after 24 h at pH 8. Based upon adsorbable organic halide formation, THMs and DXAAs, and to a lesser extent mono and trihaloacetic acids, were the majority (> 80%) of the byproducts produced for most of the aliphatic beta-dicarbonyl acid compounds. Aliphatic beta-diketone-acid-type and beta-keto-acid-type structures could be possible fast- and slow-reacting THM precursors, respectively, and aliphatic beta-keto-acid-type structures are possible slow-reacting DXAA precursors. Aliphatic beta-dicarbonyl acid moieties in natural organic matter, particularly in the hydrophilic fraction, could contribute to the significant formation of THMs and DXAAs observed after chlorination of natural waters.     

I-THM formation and speciation: preformed monochloramine versus prechlorination followed by ammonia addition

An increasing number of utilities in the United States have been switching from chlorination to chloramination practices to comply with the more stringent trihalomethane (THM) and haloacetic acid (HAA) regulations. This has important implications for disinfection byproduct (DBP) formation because the reactions of chlorine and monochloramine (NH(2)Cl) with natural organic matter (NOM) are not the same. In this study, iodinated trihalomethane (I-THM) formation from preformed NH(2)Cl and prechlorination (at two chlorine doses and contact times) followed by ammonia addition was compared. A representative bromide/iodide ratio of 10:1 was selected and four bromide/iodide levels (ambient, 50/5 or 100/10, 200/20, and 800/80 [μg/L/μg/L]) were evaluated. The results showed that I-THM formation was generally lower for prechlorination as compared to preformed NH(2)Cl due to the oxidation of iodide to iodate by chlorine. However, while prechlorination minimized iodoform (CHI(3)) formation, prechlorination sometimes formed more I-THMs as compared to preformed NH(2)Cl due to a large increase in the formation of brominated I-THM species, which were formed at much smaller amounts from preformed NH(2)Cl. I-THM concentrations and speciation for the two chloramination scenarios (i.e., preformed NH(2)Cl vs prechlorination followed by ammonia) depended on chlorine dose, contact time, bromide/iodide concentration, and NOM characteristics of the source water (SUVA(254)).     

Copper-glyphosate sorption to microcrystalline gibbsite in the presence of soluble Keggin Al13 polymers

Among the most reactive yet largely neglected adsorbents of toxicant species occurring in acidic aquatic environments are the epsilon-Keggin Al13 polyoxocations [AlO4Al12(OH)24(H2O)12(7+)], known generally as Al13 polymers. Here, we report on the sorption of Cu(II), a common ingredient of pesticides, and glyphosate {N-[phosphonomethyl]glycine (PMG)}, a widely applied herbicide, to microcrystalline gibbsite [gamma-Al(OH)3] in the presence of soluble Al13 polymers over the pH range 4-7. In the presence of gibbsite and soluble Al13 polymers, dissolved Cu(II) decreased gradually with pH, achieving a minimum at pH 5.5. Between pH 5.5 and 6.0, however, soluble Cu increased markedly, with approximately 80% of the added metal remaining in solution at pH 5.86. At pH > 6.0, soluble Cu once again decreased, becoming undetectable at pH 7. The anomalous Cu solubilization was attributed to a concomitant deprotonation of soluble Al13 polymers, yielding surface OH groups possessing high affinity for Cu(II). Removal of Cu from solution at pH > 6.0 is facilitated by flocculation of the Al13 polymers to which Cu had sorbed. The sorption behavior of the zwitterionic PMG in the presence of gibbsite and Al13 polymers was consistent with this interpretation, there being a dramatic increase in sorbed PMG at pH > 6.0 as the Al13 polymers deprotonated and flocculated. Copper and PMG loss from solution with increasing pH when both adsorptives were added to the gibbsite-Al13 polymer system was broadly similar to what was observed in the PMG-free systems, although small differences were detected in response to varying the order of adsorptive addition. The inclusion of soluble Al polymers in our experiments exposes a fundamental limitation of models based on but a single inorganic adsorbent as a means to predict the behavior of trace metals and xenobiotic organic compounds in natural systems.     

ACE-inhibitory activity of tilapia protein hydrolysates

Fish processing wastes can be used for preparing bioactive peptides with various functionalities. Our objective was to evaluate the in vitro angiotensin converting enzyme (ACE) inhibitory activity of tilapia protein hydrolysates and its corresponding fractionates. Tilapia protein was alkali-solubilised at pH 11.0 and recovered at pH 5.5 to obtain a stable substrate. This substrate was hydrolysed using two enzymes, Cryotin-F or Flavourzyme, to 7.5% and 25% degree of hydrolysis (DH). The hydrolysates were ultra-filtered into three fractions: >30 kDa fraction, 10–30 kDa fraction, and <10 kDa fractions. Both hydrolysates and fractionates were tested for ACE inhibition. Results showed that both Cryotin and Flavourzyme hydrolysates with 25% DH gave maximum ACE inhibitory activity. Low MW peptides showed higher ACE inhibition than high MW peptides. The inhibitory activity of fractionates was lower than that of the corresponding hydrolysates, possibly due to separation and removal of synergistic peptides by ultrafiltration. Amongst fractionates, all the 7.5% DH Cryotin fractions and 25% DH Flavourzyme fractions exhibited optimum % ACE inhibition. The results of this research could be used for optimising enzyme parameters to obtain peptides from tilapia with optimum in vitro ACE inhibitory activity.     

Pilot-scale in situ bioremediation of uranium in a highly contaminated aquifer. 1. Conditioning of a treatment zone

To evaluate the potential for in situ bioremediation of U(VI) to sparingly soluble U(IV), we constructed a pilot test facility at Area 3 of the U.S. Department of Energy Natural and Accelerated Bioremediation Research (NABIR) Field Research Center (FRC) in Oak Ridge, TN. The facility is adjacent to the former S-3 Ponds which received trillions of liters of acidic plating wastes. High levels of uranium are present, with up to 800 mg kg(-1) in the soil and 84-210 microM in the groundwater. Ambient groundwater has a highly buffered pH of approximately 3.4 and high levels of aluminum (12-13 mM), calcium (22-25 mM), and nitrate (80-160 mM). Adjusting the pH of groundwater to approximately 5 within the aquifer would deposit extensive aluminum hydroxide precipitate. Calcium is present in the groundwater at levels that inhibit U(VI) reduction, but its removal by injection of a high pH solution would generate clogging precipitate. Nitrate also inhibits U(VI) reduction and is present at such high concentrations that its removal by in situ denitrification would generate large amounts of N2 gas and biomass. To establish and maintain hydraulic control, we installed a four well recirculation system parallel to geologic strike, with an inner loop nested within an outer loop. For monitoring, we drilled three boreholes perpendicular to strike across the inner loop and installed multilevel sampling tubes within them. A tracer pulse with clean water established travel times and connectivity between wells and enabled the assessment of contaminant release from the soil matrix. Subsequently, a highly conductive region of the subsurface was prepared for biostimulation by removing clogging agents and inhibitors and increasing pH. For 2 months, groundwater was pumped from the hydraulically conductive zone; treated to remove aluminum, calcium, and nitrate, and supplemented with tap water; adjusted to pH 4.3-4.5; then returned to the hydraulically conductive zone. This protocol removed most of the aqueous aluminum and calcium. The pH of the injected treated water was then increased to 6.0-6.3. With additional flushing, the pH of the extracted water gradually increased to 5.5-6.0, and nitrate concentrations fell to 0.5-1.0 mM. These conditions were judged suitable for biostimulation. In a companion paper (Wu et al., Environ. Sci. Technol. 2006, 40, 3978-3987), we describe the effects of ethanol addition on in situ denitrification and U(VI) reduction and immobilization.     

Watershed sources of disinfection byproduct precursors in the Sacramento and San Joaquin Rivers, California

High levels of dissolved organic carbon (DOC) and bromide (Br) in the Sacramento and San Joaquin River waterways are of concern because DOC and Br are organic and inorganic precursors, respectively, of carcinogenic and mutagenic disinfection byproducts (DBPs). The Sacramento and San Joaquin Rivers are the two major rivers supplying water to the San Francisco Bay Delta, but sources and loads of DBP precursors into the Delta are still uncertain. The major objectives of this study were to evaluate both the quantity (DOC and Br fluxes) and the quality (reactivity in forming DBPs) of DBP precursors from the Sacramento and San Joaquin watersheds. Water samples were collected every 2 weeks at up to 35 locations along the Sacramento and San Joaquin Rivers and selected tributaries and analyzed for DOC (4 years), Br (1 year), and ultraviolet absorbance at 254 nm (1 year). Selected water samples were also tested for THM formation potential. Estimated fluxes for the Sacramento River were 39 000 +/- 12 000 Mg DOC year(-1) and 59 Mg of Br year(-1) as compared to 9000 +/- 5000 Mg of DOC year(-1) and 1302 Mg of Br year(-1) for the San Joaquin River. The THM formation potential was higher in the San Joaquin River (441 +/- 49 microg L(-1)) than the Sacramento River (176 +/- 20 microg L(-1)) because of higher concentrations of both organic (DOC = 3.62 +/- 0.14 vs 1.92 +/- 0.09 mg L(-1)) and inorganic DBP (Br = 0.80 +/- 0.07 vs < 0.03 +/- 0.01 mg L(-1)) precursors. The Sacramento River's greater DOC load despite lower DOC concentrations is due to its discharge being about 5 times greater than the San Joaquin River (50 x 10(9) vs 10 x 10(9) L day(-1)). The DOC concentration was significantly correlated with several land-cover types, including agriculture; however, no relationship was found between DOC quality and land-cover at the watershed scale.     

有机酸蒙囿硫酸铝配合物组成及结构的研究(I)

应用凝胶过滤色谱、     

Diffusive gradients in thin films sampler predicts stress in brown trout (Salmo trutta L.) exposed to aluminum in acid fresh waters

Increased levels of aluminum ions released from nutrient-poor soils affected by acid rain have been the primary cause of fish deaths in the acidified watersheds of southern Norway. The complex aluminum chemistry in water requires speciation methods to measure the gill-reactive species imposing toxic effects toward fish. Previously, aluminum speciation has mainly followed the fractionation principles outlined by Barnes/Driscoll, and several analogues of these fractionation principles have been used both in situ and in the laboratory. Due to rapid transformation processes, aluminum speciation in water samples may change even during short storage times. Thus, results obtained by laboratory fractionation methods might be misleading for the assessment of potentially toxic aluminum species in the water. Until now, all in situ field fractionation methods have been time and labor consuming. The DGT technique (diffusive gradients in thin films) is a new in situ sampler collecting a fraction of dissolved metal weighted according to the rate of diffusion and dissociation kinetics. In a field experiment with acid surface water we studied the DGT sampler as a new prediction tool for the gill accumulation of aluminum in trout (Salmo trutta L.) and the induced physiological stress responses measured as changes in blood glucose and plasma chloride. Aluminum determined with DGT (DGT-AI) was higher than labile monomeric aluminum (Ali) determined with a laboratory aluminum fractionation procedure (PCV--a pyrocatechol violet analogue of Barnes/Driscoll), a difference due to collection of a fraction of organically complexed aluminum by DGT and a reduction of the Ali fraction during sample storage. DGT-AI predicted the gill uptake and the aluminum-induced physiological stress responses (increased blood glucose and decreased plasma chloride, r2 from 0.6 to 0.9). The results indicate that DGT-AI is a better predictor for the stress response than laboratory-determined Ali, because the DGT sampler collects a more correct fraction of the gill-reactive aluminum species that induces the stress.     

Landscape control of stream water aluminum in a boreal catchment during spring flood

Inorganic aluminum (Al) concentrations are critical for defining the biological effects of acidification. The landscape's role in controlling the spatial variability of Al and its speciation has received only limited attention. We analyzed the speciation of stream Al at 14 sites within a 68 km2 boreal catchment during spring snowmelt, a period of episodic acidity. Three factors that influenced Al at these sites were landscape type (specifically the proportion of wetland areas), stream pH, and dissolved organic carbon (DOC). Forested catchment sites underlain by mineral soils had higher total Al concentrations and greater inorganic Al proportions than catchments with larger wetland areas, despite significantly higher pH. We suggest that this difference results from source limitation of Al in the peat wetlands. The control of Al solubilitywas dominated by organic complexes, with the organic carrying capacity exceeding Al in the majority of samples. When assessing the inorganic phase, only four percent of the samples were oversaturated with regards to commonly forming secondary Al minerals, with no samples showing supersaturation higher than 10 times with respect to any given solid phase. Inorganic Al rarely exceeded biological thresholds, except for short periods during peak flow in forested areas, despite two-thirds of the streams having minimum pH values below 4.9. Streams with a high percentage of wetland area were associated with lower Al:DOC ratios. The Al:DOC ratios were quite stable in each stream before, during, and after snowmelt, with the exception of isolated spikes in the Al:DOC ratio associated with particulate Al at a downstream site during high flow.     

As(III) oxidation by active chlorine and subsequent removal of As(V) by Al13 polymer coagulation using a novel dual function reagent

An electrochemically prepared water treatment reagent containing a high concentration of Al(13) polymer and active chlorine (PACC) showed promising potential for the removal of As(III) due to the combined function of oxidation and coagulation. The results indicated that PACC was effective for As(III) removal through oxidation by the active chlorine and subsequent removal of As(V) by coagulation with the Al(13) polymer. The As(III) was oxidized to As(V) by active chlorine in PACC, with a stoichiometric rate of 0.99 mg Cl(2)/mg As(III). The Al(13) polymer was the most active Al species responsible for As(V) removal in PACC. To meet As drinking water standards the stoichiometric weight ratio of Cl(2)/Al within PACC was 0.09 for the treatment of As(III). Considering the process of As(III) oxidation and As(V) coagulation together, the optimal pH conditions for the removal of As by PACC was within the neutral range, which facilitated the reaction of As(III) with active chlorine and favored the formation of Al hydroxide flocs. The presence of humic acid reduced the As(III) removal efficiency of PACC due to its negative influence on subsequent As(V) coagulation, and disinfection byproduct yields were very low in the presence of insufficient or stoichiometric active chlorine.     

Total content and speciation of aluminium in tea leaves and tea infusions

A total of 29 tea samples of different origin, 13 green tea samples, 13 black tea samples, two semi-fermented and one white tea, imported to the Czech Republic, were collected and analysed for total content of aluminium (Al) in tea leaves and tea infusions, as well as for Al compounds in these infusions. The total content of metals in tea leaves differs according to the type of tea (green or black) and is probably influenced by many factors, e.g., soil properties. The HPLC/IC speciation of Al in tea infusions was performed for all samples. The addition of Al³⁺ to the tea infusion proved that Al³⁺, Al(Y)²⁺ and Al(X)¹⁺ species can be determined in tea infusions. Increased extraction time did not show any affect on Al speciation, neither did the addition of sugar. After the addition of lemon juice, the speciation changed in one sample of black tea and five samples of green tea. These findings suggest that lemon juice as an additive can significantly influence Al speciation in tea infusions.     

Gold nanoparticle-aluminum oxide adsorbent for efficient removal of mercury species from natural waters

We report a new adsorbent for removal of mercury species. By mixing Au nanoparticles (NPs) 13 nm in diameter with aluminum oxide (Al(2)O(3)) particles 50-200 μm in diameter, Au NP-Al(2)O(3) adsorbents are easily prepared. Three adsorbents, Al(2)O(3), Au NPs, and Au NP-Al(2)O(3), were tested for removal of mercury species [Hg(2+), methylmercury (MeHg(+)), ethylmercury (EtHg(+)), and phenylmercury (PhHg(+))]. The Au NP adsorbent has a higher binding affinity (dissociation constant; K(d) = 0.3 nM) for Hg(2+) ions than the Al(2)O(3) adsorbent (K(d) = 52.9 nM). The Au NP-Al(2)O(3) adsorbent has a higher affinity for mercury species and other tested metal ions than the Al(2)O(3) and Au NP adsorbents. The Au NP-Al(2)O(3) adsorbent provides a synergic effect and, thus, is effective for removal of most tested metal ions and organic mercury species. After preconcentration of mercury ions by an Au NP-Al(2)O(3) adsorbent, analysis of mercury ions down to the subppq level in aqueous solution was performed by inductively coupled plasma mass spectrometry (ICP-MS). The Au NP-Al(2)O(3) adsorbent allows effective removal of mercury species spiked in lake water, groundwater, and seawater with efficiencies greater than 97%. We also used Al(2)O(3) and Au NP-Al(2)O(3) adsorbents sequentially for selectively removing Hg(2+) and MeHg(+) ions from water. The low-cost, effective, and stable Au NP-Al(2)O(3) adsorbent shows great potential for economical removal of various mercury species.     

Factors influencing the formation and relative distribution of haloacetic acids and trihalomethanes in drinking water

Various water quality and treatment characteristics were evaluated under controlled chlorination conditions to determine their influences on the formation and distribution of nine haloacetic acids and four trihalomethanes in drinking water. Raw waters were sampled from five water utilities and were coagulated with alum and fractionated with XAD-8 resin. The resulting four fractions--raw and coagulated water and the hydrophobic and hydrophilic extracts--were then chlorinated at pH 6 and 8 and held at 20 degrees C for various contact times. The results show that increasing pH from 6 to 8 increased trihalomethane formation but decreased trihaloacetic acid formation, with little effect on dihaloacetic acid formation. More trihalomethanes were formed than haloacetic acids at pH 8, while the reverse was true at pH 6. Hydrophobic fractions always gave higher haloacetic acid and trihalomethane formation potentials than their corresponding hydrophilic fractions, but hydrophilic carbon also played an important role in disinfection byproduct formation for waters with low humic content. The bromine-containing species comprised a higher molar proportion of the trihalomethanes than of the haloacetic acids. The hydrophilic fractions were more reactive with bromine than their corresponding hydrophobic fractions. Coagulation generally removed more haloacetic acid precursors than trihalomethane precursors. Waters with higher specific ultraviolet absorbance values were more amenable to removal of organic material by coagulation than waters with low specific ultraviolet absorbance values. Experimental evidence suggests that haloacetic acid precursors have a higher aromatic content than trihalomethane precursors.     

Chemical equilibrium modeling of organic acids, pH, aluminum, and iron in Swedish surface waters

A consistent chemical equilibrium model that calculates pH from charge balance constraints and aluminum and iron speciation in the presence of natural organic matter is presented. The model requires input data for total aluminum, iron, organic carbon, fluoride, sulfate, and charge balance ANC. The model is calibrated to pH measurements (n = 322) by adjusting the fraction of active organic matter only, which results in an error of pH prediction on average below 0.2 pH units. The small systematic discrepancy between the analytical results for the monomeric aluminum fractionation and the model results is corrected for separately for two different fractionation techniques (n = 499) and validated on a large number (n = 3419) of geographically widely spread samples all over Sweden. The resulting average error for inorganic monomeric aluminum is around 1 μM. In its present form the model is the first internally consistent modeling approach for Sweden and may now be used as a tool for environmental quality management. Soil gibbsite with a log *Ks of 8.29 at 25°C together with a pH dependent loading function that uses molar Al/C ratios describes the amount of aluminum in solution in the presence of organic matter if the pH is roughly above 6.0.     

DGT measurement of dissolved aluminum species in waters: comparing Chelex-100 and titanium dioxide-based adsorbents

Aluminum is acutely toxic, and elevated concentrations of dissolved Al can have detrimental effects on both terrestrial and aquatic ecosystems. Robust analytical methods that can determine environmentally relevant Al fractions accurately and efficiently are required by the environmental monitoring community. A simple, robust passive sampling method, the diffusive gradients in thin films (DGT) technique, was evaluated for the measurement of dissolved Al species in freshwater and marine water using either Chelex-100 or Metsorb (a titanium dioxide-based binding agent) as the adsorbent. Mass vs time DGT deployments at pH 5.05 (Al(3+) and Al(OH)(2+) dominate) and 8.35 (Al(OH)(4)(-) dominates) demonstrated linear uptake of Al (R(2) = 0.989 and 0.988, respectively) for Metsorb. Similar deployments of Chelex-DGT showed linear uptake at pH 5.05 (R(2) = 0.994); however, at pH 8.35 the mass of Al accumulated was 40-70% lower than predicted, suggesting that Chelex-100 is not suitable for Al measurements at high pH. The Metsorb-DGT measurement was independent of pH (5.0-8.5) and ionic strength (0.001-0.7 mol L(-1) NaNO(3)), whereas the Chelex-DGT measurement was only independent of ionic strength at pH 5.0. At pH 8.4, increasing ionic strength led to considerable underestimation (up to 67%) of Al concentration. Deployments of Metsorb-DGT (up to 4 days) in synthetic freshwater (pH range 5.4-8.1) and synthetic seawater (pH 8.15) resulted in linear mass uptakes, and the concentration measured by DGT agreed well with solution concentrations. Conversely, deployment of Chelex-DGT in synthetic seawater and freshwater (pH ≥7.7 Al(OH)(4)(-) dominant species) resulted in a decrease in accumulated mass with increasing deployment time. In situ field evaluations in fresh, estuarine, and marine waters confirmed that Metsorb-DGT was more accurate than Chelex-DGT for the measurement of dissolved Al in typical environmental waters.