Influence of sorption to dissolved humic substances on transformation reactions of hydrophobic organic compounds in water. Part II: hydrolysis reactions

The effect of dissolved humic acid (HA) on two types of hydrolysis reactions was investigated: (I) dehydrochlorination of gamma-hexachlorocyclohexane (HCH) and 1,1,2,2-tetrachloroethane (TeCA) as a reaction involving hydroxide ions (OH(-)) and (II) hydrolysis of 1-octyl acetate (OA) which is catalyzed by H(+) at the applied pH value (pH 4.5). The rate of TeCA hydrolysis was not affected by addition of 2 g l(-1) of HA at pH 10 (k' = 0.33 h(-1)) but HCH hydrolysis was significantly inhibited (k' = 4.6 x 10(-3) h(-1) without HA and 2.8 x 10(-3)h(-1) at 2 g l(-1) HA). HCH is sorbed by 51% whereas TeCA sorption is insignificant at this HA concentration. Sorbed HCH molecules are effectively protected due to electrostatic repulsion of OH(-) by the net negative charge of the HA molecules. In contrast, OA hydrolysis at pH 4.5 (k' = 1.6 x 10(-5) h(-1)) was drastically accelerated after addition of 2 g l(-1) HA (k' = 1.1 x 10(-3) h(-1)). The ratio of the pseudo-first-order rate constants of the sorbed and the freely dissolved ester fraction is about 70. H(+) accumulation in the microenvironment of the negatively charged HA molecules was suggested to contribute to the higher reaction rate for the sorbed fraction in case of this H(+)-catalyzed reaction. Analogous effects from anionic surfactants are known as micellar catalysis.     

Colloid-facilitated transport of lead in natural discrete fractures

Colloid-facilitated transport of lead (Pb) was explored in a natural chalk fracture with an average equivalent hydraulic aperture of 139 μm. Tracer solution was prepared by adding montmorillonite (100 mg L^?1) and/or humic acid (HA) (10 mg L^?1) to modified artificial rainwater containing dissolved Pb (21.4 mg Pb L^?1), naturally precipitated PbCO₃ particles (16.4 mg Pb L^?1) and LiBr (39.0 mg L^?1). We found that Pb is only mobile when associated with colloids. PbCO₃ particles were not mobile in the fracture. The addition of HA to the montmorillonite suspension increased the suspension's mobility and therefore promoted the colloid-facilitated transport of Pb. The increases in pH and sodium absorption ratio induced by the chalk-tracer solution interactions appeared to increase the dispersion and mobilization of colloids entering the fracture. The dominant colloid-facilitated transport of Pb reported in this study has significant implications for risk assessment of Pb mobility in fractured rocks.     

Formation of leadhillite and calcium lead silicate hydrate (C-Pb-S-H) in the solidification/stabilization of lead contaminants

In this study, we have investigated the structure of Pb-doped solidified waste forms (SWF) for assessment of lead fixation. A large quantity of lead precipitates produced during the S/S, based upon the results of cement-water solution analysis, X-ray diffraction and electron probe microanalysis/electron dispersive spectroscopy investigations, have been shown to be principally leadhillite (lead carbonate sulfate hydroxide, Pb(4)SO(4)(CO(3))(2)(OH)(2)), lead carbonate hydroxide hydrate (3PbCO(3).2Pb(OH)(2).H(2)O) and two other unidentified lead salts. In the long curing, the lead species dissolved from the lead precipitates are fixed into the cement matrix, forming a gelling calcium lead silicate hydrate during cement-based solidification. On leaching the lead precipitates such as leadhillite were markedly dissolved/released and some dissolved lead species were adsorbed to silicate-rich surface of leached SWF with the subsequent formation of mainly amorphous gel of calcium lead silicate hydrate.     

Lead phosphate formation in soils

Pyromorphite (Pb5(PO4)3Cl) is one of the most thermodynamically stable lead minerals under the geochemical conditions prevailing in the surface environment. It is therefore expected to form in soils contaminated with Pb if sufficient phosphorus is available. Pyromorphite has previously been identified in mine-waste and industrially contaminated soils but has not previously been identified in urban soils. This paper reports on the presence of a Pb phosphate in urban and roadside soils. This phase has formed in the soil as a weathering product of Pb-bearing grains. Quantitative EDX analyses indicated that the Pb phosphate phase is pyromorphite with Ca frequently substituting for Pb between 21-31 atomic percent. However, positive identification of this phase by XRD was hindered by the deviation from pure end-member and possibly also by the poorly crystalline nature of the phase. Pyromorphite accounted for less than 2% of the total Pb in these soils. However, phosphate amendments to the soil could induce further formation of pyromorphite. As pyromorphite is a highly insoluble mineral, this may be effective in reducing the bioavailability of Pb in urban soils.     

Pb remobilization by bacterially mediated dissolution of pyromorphite Pb5(PO4)3Cl in presence of phosphate-solubilizing Pseudomonas putida

Remediation of lead (Pb)-contaminated sites with phosphate amendments is one of the best studied and cost-effective methods for in situ immobilization. In this treatment, a very stable mineral, pyromorphite Pb₅(PO₄)₃Cl, is formed. Several studies propose to improve this treatment method with the addition of phosphate-solubilizing bacteria (PSB). The effect of bacteria on solubilization of pyromorphite is unknown. In this study, the effect of the soil microorganisms on the stability of pyromorphite Pb₅(PO₄)₃Cl has been investigated in a set of batch solution experiments. The mineral was reacted with Pseudomonas putida, a common soil microorganism. Dissolution of pyromorphite was enhanced by the presence of P. putida, resulting in an elevated Pb concentration in the solution. This occurred even when the bacteria were provided with an additional source of phosphate in the solution. Pyromorphite has been shown to be a potential source of nutrient phosphorus for common soil bacteria. Thus, the use of PSB in remediation treatments of Pb contaminated sites may have adverse long-term impacts on Pb immobilization. Conscious phosphate management is suggested for long-term sustainability of the in situ Pb immobilization by pyromorphite formation.     

Removal of aqueous lead by poorly-crystalline hydroxyapatites

The use of a phosphorus amendment in altering Pb to a chemically less mobile phase is a promising strategy based on minimizing ecotoxicological risk and improving time and cost efficiency. This study evaluated crystalline and poorly-crystalline hydroxyapatite sorbents on removal of aqueous Pb in response to reaction time, solution pH, and Pb concentration. Batch experiments were conducted using a commercially-available crystalline hydroxyapatite (HA), and two poorly-crystalline hydroxyapatites synthesized from gypsum waste (CHA) and incinerated ash of poultry waste (MHA). Poorly-crystalline hydroxyapatites had greater capacity for Pb removal from a solution with a wider pH range as compared to a crystalline hydroxyapatite. The maximum sorption capacity of Pb determined by the Langmuir model was 500 mg g⁻¹ for CHA, 277 mg g⁻¹ for MHA and 145 mg g⁻¹ for HA. Removal of aqueous Pb by CHA was not dependent on solution pH, with a 98.8% reduction throughout the solution pH range of 2–9, whereas aqueous Pb removal by HA and MHA was pH-dependent with less removal in the neutral solution pH. Poorly-crystalline hydroxyapatites may provide an effective alternative to existing remediation technologies for Pb-contaminated sites.     

Effect of overlying water pH, dissolved oxygen, salinity and sediment disturbances on metal release and sequestration from metal contaminated marine sediments

Experiments were undertaken to examine the key variables affecting metal release and sequestration processes in marine sediments with metal concentrations in sediments reaching up to 86, 240, 700, and 3000 mg kg(-1) (dry weight) for Cd, Cu, Pb and Zn, respectively. The metal release and sequestration rates were affected to a much greater extent by changes in overlying water pH (5.5-8.0) and sediment disturbance (by physical mixing) than by changes in dissolved oxygen concentration (3-8 mg l(-1)) or salinity (15-45 practical salinity units). The physical disturbance of sediments was also found to release metals more rapidly than biological disturbance (bioturbation). The rate of oxidative precipitation of released iron and manganese increased as pH decreased and appeared to greatly influence the sequestration rate of released lead and zinc. Released metals were sequestered less rapidly in waters with lower dissolved oxygen concentrations. Sediments bioturbated by the benthic bivalve Tellina deltoidalis caused metal release from the pore waters and higher concentrations of iron and manganese in overlying waters than non-bioturbated sediments. During 21-day sediment exposures, T. deltoidalis accumulated significantly higher tissue concentrations of cadmium, lead and zinc from the metal contaminated sediments compared to controls. This study suggests that despite the fact that lead and zinc were most likely bound as sulfide phases in deeper sediments, the metals maintain their bioavailability because of the continued cycling between pore waters and surface sediments due to physical mixing and bioturbation.     

Distribution of soil arsenic species, lead and arsenic bound to humic acid molar mass fractions in a contaminated apple orchard

Excessive application of lead arsenate pesticides in apple orchards during the early 1900s has led to the accumulation of lead and arsenic in these soils. Lead and arsenic bound to soil humic acids (HA) and soil arsenic species in a western Massachusetts apple orchard was investigated. The metal-humate binding profiles of Pb and As were analyzed with size exclusion chromatography-inductively coupled plasma mass spectrometry (SEC-ICP-MS). It was observed that both Pb and As bind "tightly" to soil HA molar mass fractions. The surface soils of the apple orchard contained a ratio of about 14:1 of water soluble As (V) to As (III), while mono-methyl (MMA) and di-methyl arsenic (DMA) were not detectable. The control soil contained comparatively very low levels of As (III) and As (V). The analysis of soil core samples demonstrated that As (III) and As (V) species are confined to the top 20 cm of the soil.     

Dechlorination of hexachlorobenzene using lead–iron bimetallic particles

Synthesized lead–iron (Pb/Fe) bimetallic particles were applied to dechlorinate hexachlorobenzene (HCB) under various conditions (e.g. bimetal amount, initial pH value, reaction temperature, and reaction duration). The results showed that adding Pb onto Fe benefited the dechlorination of HCB and the bimetal with 1.4% Pb content performed best. The degradation rate decreased regularly as the initial pH value of the aqueous increased from 1.9 to 11.1 except for pH 7.0 where the fastest dechlorination rate emerged. The dechlorination could be enhanced by increasing the amount of Pb/Fe or the reaction temperature. The dechlorination ratio of HCB within 15 min increased from 24.3% to 81.3% when Pb/Fe amount increased from 0.1 g to 0.8 g. The dechlorination followed pseudo-first-order kinetics, and the dechlorination rate constants were 0.0027, 0.0064, 0.0157, and 0.0321 min^?1 at 25, 50, 70, and 85 °C, respectively, and the activation energy (E_a) of the dechlorination by Pb/Fe was 37.86 kJ mol^?1.     

Removal of aqueous lead by poorly-crystalline hydroxyapatites

The use of a phosphorus amendment in altering Pb to a chemically less mobile phase is a promising strategy based on minimizing ecotoxicological risk and improving time and cost efficiency. This study evaluated crystalline and poorly-crystalline hydroxyapatite sorbents on removal of aqueous Pb in response to reaction time, solution pH, and Pb concentration. Batch experiments were conducted using a commercially-available crystalline hydroxyapatite (HA), and two poorly-crystalline hydroxyapatites synthesized from gypsum waste (CHA) and incinerated ash of poultry waste (MHA). Poorly-crystalline hydroxyapatites had greater capacity for Pb removal from a solution with a wider pH range as compared to a crystalline hydroxyapatite. The maximum sorption capacity of Pb determined by the Langmuir model was 500 mg g⁻¹ for CHA, 277 mg g⁻¹ for MHA and 145 mg g⁻¹ for HA. Removal of aqueous Pb by CHA was not dependent on solution pH, with a 98.8% reduction throughout the solution pH range of 2–9, whereas aqueous Pb removal by HA and MHA was pH-dependent with less removal in the neutral solution pH. Poorly-crystalline hydroxyapatites may provide an effective alternative to existing remediation technologies for Pb-contaminated sites.     

Control of lead solubility in soil contaminated with lead shot: effect of soil pH

An incubation experiment was carried out to assess the rate of oxidation of Pb shot and subsequent transfer of Pb to the soil under a range of soil pH conditions. Lead shot corrosion was rapid, so that soil solution and fine earth (<1mm) Pb concentrations increased rapidly within a few months. Corrosion products, dominated by hydrocerussite (Pb(3)(CO(3))(2)(OH)(2)), developed in crusts surrounding individual Pb pellets. However, irrespective of pH, Pb(2+) activities in the soil solutions, modelled using WHAM 6, were much lower than would be the case if they were controlled by the solubility of the dominant Pb compounds present in the Pb shot crust material. In contrast, modelling of soil solid-solution phase distribution of Pb, again using WHAM 6, suggested that, at least during the 24 months of the study, soil solution Pb concentrations were more likely to be controlled by sorption of Pb by the soil solid phase.     

Competitive effect of iron(III) on metal complexation by humic substances: characterisation of ageing processes

Aiming at an assessment of counteractive effects on colloid-borne migration of actinides in the event of release from an underground repository, competition by Fe(III) in respect of metal complexation by dissolved organic matter was investigated for the example of Eu(III) as an analogue of trivalent actinides. Complexation with different humic materials was examined in cation exchange experiments, using (59)Fe and (152)Eu as radioactive tracers for measurements in dilute systems as encountered in nature. Competitive effects proved to be significant when Fe is present at micromolar concentrations. Flocculation as a limiting process was attributed to charge compensation of humic colloids. Fe fractions bound to humic acids (HA) were higher than 90%, exceeding the capacity of binding sites at high Fe concentrations. It is thus concluded that the polynuclear structure of hydrolysed Fe(III) is maintained when bound to HA, which is also inferred from UV-Vis spectrometry. The competitive effect was found to be enhanced if Fe and HA were in contact before Eu was added. Depending on the time of Fe/HA pre-equilibration, Eu complexation decreased asymptotically over a time period of several weeks, the amount of bound Fe being unchanged. Time-dependent observations of UV-Vis spectra and pH values revealed that the ageing effect was due to a decline in Fe hydrolysis rather than structural changes within HA molecules. Fe polycations are slowly degraded in contact with humic colloids, and more binding sites are occupied as a consequence of dispersion. The extent of degradation as derived from pH shifts depended on the Fe/HA ratio.     

北运河表层沉积物对重金属Cu、Pb、Zn的吸附

首先分析了北运河6个采样点表层沉积物中重金属含量及相关基本特征。通过实验室模拟实验,利用分配系数Kd评价沉积物对重金属Cu、Pb、Zn的吸附特性,进一步考察了水体pH变化和有机质对重金属在北运河沉积物上吸附的影响。结果表明,沉积物中重金属的含量顺序为Zn>Cu>Pb,去除有机质后,沉积物对重金属的吸附能力显著降低,但各采样点中的重金属含量,沉积物对重金属吸附能力,以及沉积物中的有机质含量并没有明显相关性,这可能是因为不同采样点中有机质种类与结构不同导致的。总之,北运河沉积物对Pb有很强的吸附能力,其次是Cu和Zn,而且,Cu、Zn、Pb的吸附量随着pH的升高逐渐增大,水体pH值对于Zn的吸附影响更大。     

Effects of organic acids on adsorption of lead onto montmorillonite,goethite and humic acid

Adsorption isotherms for Pb onto six soil components (quartz, feldspar, kaolinite, montmorillonite, goethite and humic acid) were studied. The influence of pH, EDTA and citric acid on the adsorption of Pb onto montmorillonite, goethite and humic acid were considered. Results indicate that the experimental data fit the Langmuir Adsorption Isotherm. The adsorption capacity for Pb at pH 6 was found to be in the order: humic acid (22.7 mg g(-1)) > goethite (11.04 mg g(-1)) > montmorillonite (10.4 mg g(-1)) > kaolinite (0.91 mg g(-1)) > feldspar (0.503 mg g(-1)) > quartz (0.148 mg g(-1)). Generally, the amount of Pb adsorbed onto montmorillonite, goethite and humic acid decreased with increasing concentrations of EDTA and citric acid and with increases in alkality. However, there were two exceptions: (1) addition of citric acid increased the amount of Pb adsorbed onto humic acid; and (2) the amount of Pb adsorbed onto goethite decreased with increasing pH in the presence of EDTA. Some mechanisms involved in the adsorption reactions are discussed.     

Lead contamination in tea garden soils and factors affecting its bioavailability

The consumption of heavy metals is detrimental to human health and most countries restrict the concentration of metals such as lead (Pb) in food and beverages. Recent tests have detected high Pb concentrations in certain commercial brands of tea leaves and this finding has raised concerns for both producers and consumers. To investigate what factors may be contributing to the increase in Pb accumulation in the tea leaves we collected tea leaves and soils from tea producing areas and analyzed them for Pb concentration, pH and organic matter content. The result showed the Pb concentration of 47% investigated tea leaves samples was beyond 2 mg kg(-1), the permissible levels given by China. The total Pb concentration in the surface and subsurface soil layers averaged 36.4 and 32.2 mg kg(-1), respectively which fall below of the 60 mg kg(-1) limit provided for organic tea gardens in China. The pH of the tea garden soils was severely acidic with the lowest pH of 3.37. Soils under older tea gardens tended to have a lower pH and a higher Pb bioavailability which was defined as the amount of lead extracted by CaCl2 solution than those under younger tea gardens. We found that the concentration of bioavailable Pb and the percentage of bioavailable Pb (bioavailable Pb relative to total Pb concentration) were positively correlated with soil H+ activity and soil organic matter content, and the organic matter accumulation contribute more effects on Pb bioavailability in these two factors. We conclude that soil acidification and organic matter accumulation could contribute to increasing Pb bioavailability in soil and that these could increase Pb uptake and accumulation in the tea leaves.     

Relation of enhanced Pb solubility to Fe partitioning in soils

It is well documented that Pb solubility may be related to Fe chemistry in soils and enhanced Pb solubility may occur under certain reducing conditions; however, quantification of such relationships is unavailable. Based on metal classification, Pb (II) and Fe (II) are similar in some chemical characteristics. Thus, competition between Pb and Fe for ligands in soils may be important in determining Pb solubility. In this paper, Pb solubility was examined in a sandy soil after spiking with Pb and incubating for 40 days under water-flooded or non-water-flooded conditions. Solution chemistry in soil columns was adjusted using different concentrations of NaCl, CaCl(2) and deionized water of varying pH before incubation. The results showed that Pb solubility in the soil was not correlated well with pH, dissolved organic C or aqueous Fe concentrations. However, an index of Fe partition behavior using the ratio of aqueous Fe to sorbed Fe was related to Pb solubility. Enhanced Pb solubility occurred only when the index was < approximately 2 kg l(-1). The index can be a simple measure of Fe's ability to compete with Pb for ligands in solution. The ability of Fe to compete with Pb decreases as the index decreases and as the ratio approached its minimum, substantial increases in Pb solubility will be expected. In general, the index was not sensitive to changes in solution chemistry. A similar trend was observed using one data set published in the literature.     

Selective separation of copper(II) and nickel(II) from aqueous media using the complexation-ultrafiltration process

The polyethylenimine (PEI) as complexing agent was used to study the complexation-ultrafiltration (CP-UF) process in the selective removal of Cu(II) from Ni(II) contained in aqueous media. Preliminary tests showed that optimal chemical conditions for Cu(II) and Ni(II) complexation by the PEI polymer were pH>6.0 and 8.0, respectively, and polymer/metal weight ratio of 3.0 and 6.0, respectively. The effect of some important operating parameters on process selectivity was studied by performing UF tests at different parameters: pH, polymer/metal weight ratio, transmembrane pressure (TMP), and membrane cut-off in a batch experimental set-up. It was observed that process selectivity was achieved by choosing the pH value for obtaining a preferential copper complexation (pH 6.0), and the polymer/metal ratio needed to bound only the copper ion (3.0). The selective separation by UF tests was performed by using both a laboratory aqueous solution and a real aqueous effluent (water from Emoli torrent, Rende (CS)). The Iris 30 membrane at TMP of 200 kPa (2 bar) for both aqueous media gave the best results. A complete nickel recovery was reached, and copper recovery was the highest for this membrane (94% and 92%). Besides at this pressure, a lower water amount was needed to obtain total nickel recovery by diafiltration. A little higher membrane fouling was obtained by using the river effluent due to the presence of dissolved organic and inorganic matter.     

Metal ion removal from water by sorption on paper mill sludge

Chromatographic columns packed with paper mill sludge are employed for metal ion recovery from water. The breakthrough curves show that cadmium, copper, lead and silver are removed from acid solutions (pH 2, 4); the affinity series is Pb(II)>Cu(II)>Ag(I)>Cd(II). Both the amount of metal retained and the metal-matrix interaction are pH dependent; the sorptive capacity increases with increasing pH. When the metals are present together at the same initial concentrations a competition among the different ions occurs although the affinity order remains unchanged. In metal recovery from the paper mill sludge column, the total amount of the cadmium and copper is displaced by HCl 1.0 M, 65% of the lead by HCl 0.1 M and 75% of the silver by HNO(3) 0.1 M. More than 95% of copper and lead and less than 20% of cadmium were recovered with HCl 0.1 M when the metals were present at the same time.     

Solubility of lead, zinc and copper added to mineral soils

Elevated levels of heavy metals in soils are a result of industrial activities, atmospheric deposition, and the land application of sewage sludges and industrial by-products. Their persistence in the soil environment has created interest in the possible changes in solubility. In this study, total dissolved concentrations of Pb, Zn, and Cu were monitored in seven metal-amended soils (a calcareous and six acid mineral soils). Single metal solutions were added to soils and equilibrated (aged) for 40 days. During the 40 days the soil was allowed to air-dry and was rewetted in cycles of about 5 days. At the end of this reaction period, metal solubility was measured (by atomic absorption spectrometry and direct current plasma spectrometry) at the initial soil pH and at decreased pH values which were induced by addition of small aliquots of acid. As expected, solubility of added Pb, Zn, and Cu increased with a decrease in pH. Furthermore, the results showed that the solubility relationship with pH was similar in all non-calcareous soils. This suggests that metal solubility may be controlled by similar soil components, presumably involving soil characteristics such as pH, organic matter content, and soil mineralogy. For each metal, an approximate pH value was found at which solubility deviated from the solubility of metals when they occur in soils at typical (natural) values. This pH was about (pH+/-0.2): 5.2 for Pb, 6.2 for Zn, and 5.5 for Cu. Thus, pH values below these thresholds may enhance metal mobility, biological availability and toxicity in soils. Metals dissolved at higher pH in the calcareous soil (18.8 g kg(-1) inorganic carbon, initial pH 8.2). In a calcareous soil, a significant fraction of these metals react with carbonates, and decreased pH results in much higher metal dissolution. Yet, metal solubility in soils is not determined by the formation and dissolution of single metal compounds.     

Predicting Pb bioavailability to freshwater microalgae in the presence of fulvic acid: algal cell density as a variable

In order to better understand the relationship between lead speciation and its bioavailability in natural waters, the interactions between Pb(II), fulvic acid and the freshwater alga, Chlorella kesslerii were studied at various algal cell densities. An increase in cellular lead or fulvic acid adsorbed to algae was observed with decrease of the cell density from ca. 10(7) to 10(5)cells ml(-1). In the presence of fulvic acid, cellular Pb was greater than that expected for the same free lead ion concentrations in the absence of fulvic acid in agreement to our previous study. This effect was found to be more pronounced at lower cell density, in accordance with increased fulvic acid adsorption to algae. Good fit between experimental observations and model predictions of cellular Pb at various cell densities, was observed by assuming that fulvic acid adsorbed to algae give rise to additional binding sites for Pb(II). The findings of this study indicate that a further extension of the biotic ligand model which includes the formation of a ternary complex and cell density (or concentration) as an input parameter is needed to improve its site-specific predictive capacity, especially in the case of dissolved organic matter-rich surface waters. This extension of predictive capacity would allow to reduce the deviations from the BLM model predictions for microalgae in the presence of dissolved organic matter and hence will serve as a mechanistic tool for establishing ambient site-specific water quality criteria.