有机锡化合物的污染及其毒性

为了解有机锡化合物污染及其毒性的研究成果，从有机锡化合物对海洋的污染状况、污染来源、有机锡化物对海洋生物以及人体健康的毒性等方面进行了综述。实验证明有机锡化合物尤其是三苯基锡和三丁基锡，能够引起雌性软体动物变性、哺乳细胞生殖毒性、以及人体免疫毒性等。有机锡化合物作为一种防污涂料技广泛应用于船体和海洋建筑等，因此导致了海产品中残留了大量的有机锡化合物，这些化合物可以通过食物链影响人体健康。人类食用了合有机锡化合物的海产品后，对人体健康可能造成的潜在危险，其危害机理尚需进一步研究。     

Retrospective monitoring of organotin compounds in marine biota from 1985 to 1999: results from the German Environmental Specimen Bank

In archived samples from the German Environmental Specimen Bank, organotin compounds including tributyltin (TBT) and triphenyltin (TPT) as well as their degradation products were quantified. Biota samples from North Sea and Baltic Sea areas were analyzed by gas chromatography/atomic emission detection-coupling after extraction and Grignard or ethylborate derivatization. TBT and TPT were detected in nearly all samples. A decrease of TPT contamination was observed in bladder wrack, common mussels, and eelpout muscle tissues in the period 1985-1999. In this period, TPT concentrations in North Sea mussels decreased from 98 to 7 ng/g (as organotin cation concentration in wet tissue). Concentrations of TBT remained relatively constant with 17 +/- 3 ng/g for mussels from a site with nearby marine traffic and 8 +/- 2 ng/g for a more remote area. The results reflect that TBT is still used as a biocide in antifouling paints whereas the use of TPT as a co-toxicant in such preparations had been ceased in the 1980s. The fact that the use of TBT in antifouling paints was banned in 1991 for small boats within the European Community seems not to have resulted in a decrease of TBT levels in marine biota.     

Trophic magnification of triphenyltin in a marine food web of Bohai Bay, North China: comparison to tributyltin

Organotins, especially tributyltin (TBT) and triphenyltin (TPT), are of particular concern due to their ubiquity in the aquatic environment and theirtoxicityto aquatic organisms. This study reports field studies on trophic magnification factors (TMF) of TBT and TPT in a marine food web. TBT, TPT, and their metabolites in plankton, five benthic invertebrate species, and six fish species collected from Bohai Bay, North China were determined, and it was found that the concentrations of TPT in marine fish were unexpectedly higherthan those of TBT. A positive relationship was found between trophic levels and concentrations of TPT, indicating trophic magnification of TPT in this food web. The TMF of TPT was calculated to be 3.70. On the other hand, concentrations of TBT, dibutyltin (DBT) and monobutyltin (MBT) did not exhibit statistically significant trends with trophic levels, and the TMF of TBT was 0.59. Analysis of organotins in the water and surface sediment from Bohai Bay revealed low inputs of TPT to the environment, which indicated that the high concentrations of TPT found in fish from Bohai Bay were due to the food web magnification of TPT.     

Organotin pollution in deep-sea fish from the northwestern Mediterranean

Aquatic pollution resulting from extensive usage of organotin compounds has been of great concern due to their deleterious effects in nontarget organisms. However, organotin contamination in deep-sea ecosystems has been rarely studied. The presentwork attempted to determine butyltin and phenyltin compounds in deep-sea fish collected between 1000 and 1800 m depth in the NW Mediterranean. The concentration of tributyltin (TBT) and its degradation products, mono- (MBT) and dibutyltin (DBT), aswell astriphenyltin (TPT),and mono- anddiphenyltin (MPT, DPT) was determined in different tissues (liver, gills, digestive tube, and muscle) of several fish species. Total butyltin residues were up to 175 ng/g wet wt, and they were comparable to levels found in coastal fish collected along the Catalan coast. In contrast, deep-sea fish contained much higher levels of phenyltins (up to 1700 ng/g wet wt), and particularly TPT (up to 1430 ng/g wet wt), than previously reported concentrations in shallow-water organisms. The obtained results confirm the long-range transport of organotin compounds to the deep-sea environment, and the subsequent exposure of fish inhabiting nonpoint source areas. The use of TPT in agriculture or as an antifouling agent, its transport to the deep-sea environment associated to particulate matter, and its nonbiodegradable nature in the food chain may account for the high residue levels detected in deep-sea organisms.     

pH dependence of the partitioning of triphenyltin and tributyltin between phosphatidylcholine liposomes and water

Triorganotin compounds are very toxic contaminants. The site of their basic mechanism of action of acute toxicity is the biomembrane. Liposome-water distribution ratios of triphenyltin and tributyltin were determined between pH 3 and pH 8 with the equilibrium dialysis method in the micromolar concentration range, which is the concentration range where acute toxicity is observed. In addition, biomembrane-water distribution ratios of tributyltin were determined with chromatophores of Rhodobacter sphaeroides that contain approximately 70% protein intercalated in the lipid bilayer. The liposome-water distribution of both compounds showed only weak pH dependence. For tributyltin, the apparent distribution ratio decreased from 4100 at low pH to 2000 at high pH, while this ratio decreased from 70 000 to 22 000 for TPT. The distribution ratio of the triorganotin cation exceeded that of the neutral hydroxo complex by a factor of 2. The distribution ratio of both the cation and the hydroxo complex of triphenyltin exceeded that of tributyltin by a factor of 10. It is postulated that the sorption of the cation is governed by complex formation with ligands in the phospholipids, presumably the phosphate group. The biomembrane-water distribution ratio of tributyltin was found to be lower than the liposome-water distribution ratio at high pH. The hydroxo complex appears to partition only to the lipid fraction of the biomembrane. Yet, at low pH the biomembrane-water distribution ratio exceeded the liposome-water distribution ratio, which is attributed to complex formation of the cationic species with ligands of the protein fraction.     

Biotransformation of tributyltin to tin in freshwater river-bed sediments contaminated by an organotin release

The largest documented release of organotin compounds to a freshwater river system in the United States occurred in early 2000 in central South Carolina. The release consisted of an unknown volume of various organotin compounds such tetrabutyltin (TTBT), tributyltin (TBT), tetraoctyltin (TTOT), and trioctyl tin (TOT) and resulted in a massive fish kill and the permanent closures of a municipal wastewater treatment plant and a local city's only drinking-water intake. Initial sampling events in 2000 and 2001 indicated that concentrations of the ecologically toxic TTBT and TBT were each greater than 10 000 microg/kg in surface-water bed sediments in depositional areas, such as lakes and beaver ponds downstream of the release. Bed-sediment samples collected between 2001 and 2003, however, revealed a substantial decrease in bed-sediment organotin concentrations and an increase in concentrations of degradation intermediate compounds. For example, in bed sediments of a representative beaver pond located about 1.6 km downstream of the release, total organotin concentrations [the sum of TTBT, TBT, and the TBT degradation intermediates dibutyltin (DBT) and monobutyltin (MBT)] decreased from 38 670 to 298 microg/kg. In Crystal Lake, a large lake about 0.4 km downstream from the beaver pond, total organotin concentrations decreased from 28 300 to less than 5 microg/kg during the same time period. Moreover, bed-sediment inorganic tin concentrations increased from pre-release levels of less than 800 to 32 700 microg/kg during this time. These field data suggest that the released organotin compounds, such as TBT, are being transformed into inorganic tin by bed-sediment microbial processes. Microcosms were created in the laboratory that contained bed sediment from the two sites and were amended with tributyltin (as tributyltin chloride) under an ambient air headspace and sacrificially analyzed periodically for TBT, the biodegradation intermediates DBT and MBT, and tin. TBT concentrations decreased faster [half-life (t1/2) = 28 d] in the organic-rich sediments (21.5%) that characterized the beaver pond as compared to the slower (t1/2 = 78 d) degradation rate in the sandy, organic-poor, sediments (0.43%) of Crystal Lake. Moreover, the concentration of inorganic tin increased in microcosms containing bed sediments from both locations. These field and laboratory results suggest that biotransformation of the released organotins, in particular the ecologically detrimental TBT, does occur in this fresh surface-water system impacted with high concentrations of neat organotin compounds.     

Sorption and desorption behavior of tributyltin with natural sediments

Tributyltin (TBT) sorption to four natural sediment samples in artificial seawater was examined under a range of modified pH and salinity conditions. Three of the sediment samples were relatively pristine with regard to TBT contamination, but the fourth was a TBT-contaminated sediment from a commercial marina. Sorption of TBT was described well by linear sorption isotherms, with distribution coefficients ranging from 6.1 to 5210 L/kg depending on the pH and salinity. The sediment organic C content and particle size distribution were important determinants of sorption behavior. The presence of resident TBT in the contaminated marina sediment caused a substantial reduction in further TBT sorption. Desorption of TBT from the marina sediment was described by relatively large observed distribution coefficients ranging from 5100 to 9400 L/kg, suggesting that aging effects may reduce sorption reversibility. Increased artificial seawater salinity generally reduced TBT sorption at pH 4 and 6, but enhanced TBT sorption at pH 8. Regardless of salinity, maximum sorption of TBT was observed at pH 6, which is attributed to an optimal balance between the abundance of cationic TBT+ species and deprotonated surface ligands. Consideration of aqueous TBT speciation along with octanol-water partitioning behavior suggests that hydrophobic partitioning of TBTCl(0) to nonpolar organic matter was important for pH < 6, while partitioning of TBTOH(0) was important at higher pH.     

TiO2 nanoparticles in the marine environment: impact on the toxicity of tributyltin to abalone (Haliotis diversicolor supertexta) embryos

Little information is available on the potential ecotoxicity of manufactured nanomaterials (MNMs) in the marine environment. To carefully address this issue, the toxicity of nanosized titanium dioxide (nTiO(2)) aggregates in the marine environment was evaluated using abalone (Haliotis diversicolor supertexta) embryonic development as a model. The effect of nTiO(2) aggregates on the toxicity of the highly toxic marine antifouling compound tributyltin (TBT) to abalone embryos was also investigated. No developmental effects of nTiO(2) were observed at 2 mg/L but concentrations ≥10 mg/L caused hatching inhibition and malformations. The presence of 2 mg/L nTiO(2) increased the toxicity of TBT up to 20-fold compared with TBT alone. This enhancement of TBT may be due to the combined effects of TBT adsorption onto nTiO(2) aggregates and the internalization of nTiO(2) aggregates by abalone embryos. These observations indicate that MNMs may have important indirect impacts on aquatic organisms by varying the toxicity of coexisting pollutants. Thus, risk assessments for MNMs should consider both their direct effects and possible indirect effects of interactions with other environmental contaminants.     

Effect of solid surface composition on the migration of tributyltin in groundwater

Tributyltin (TBT) is the most important organotin compound that has been introduced into aquatic ecosystems. A better understanding of its interactions with solid surfaces is essential to estimate the possibilities of TBT migration through subsurface environments. For this purpose, TBT sorption onto a porous matrix of natural origin, a quartz sand as an aquifer material, was studied at low concentration levels with a monodirectional model of column type allowing sequential investigation of sorption and desorption processes. Different treatments of the solid phase were performed by injecting alkaline solutions, NaOH at pH 10.8 or NaClO-NaCl at pH 11.5, by decreasing the ionic strength or by adding kaolinite to change the surface composition and properties. The removal of iron and aluminum (hydr)oxides from the sand surface did not affect so much the sorption (decrease in 14% as compared to sorption on the raw sand). The original use of X-ray photoelectron spectroscopy to control treatment efficiency and to characterize sand surface modifications permitted to relate TBT sorption onto the aquifer material to quartz, the main component of the sand, and clay minerals (mainly kaolinite) present at trace levels at the sand surface. A first attempt of transport modeling with these two surface sites showed the consistency of our assumption. Moreover, estimation of Langmuir-type constants showed that TBT sorption affinity for the quartz surface (KL = 26.7 L micromol(-1)) was much greater than for kaolinite (KL = 6.3 L micromol(-1)).     

海洋生物中砷脂形态分析及毒性评价研究进展

砷是一种有毒类金属,已被确定为人类致癌物,砷中毒会造成人体多种健康问题。砷可以分为无机砷和有机砷,一般认为无机砷毒性大于有机砷。砷脂属于有机砷,广泛存在于海洋生物组织中。之前的研究认为砷脂毒性极低,但近年来随着科学技术的进步与发展,对砷脂的研究越来越深入,砷脂的形态分析和毒性评价也逐步成为热点。目前已知的砷脂主要包括含砷脂肪酸、含砷碳氢化合物和含砷磷脂3种形态,且不同形态之间毒性各不相同。但由于其形态结构复杂、生物利用度低、含量低以及提取和检测难度高等原因,砷脂毒性作用机制尚不明确。因此,本文综述了海洋生物中砷脂主要形态的分析方法和毒性评价的最新研究进展,以期为进一步阐明砷脂的形态、毒性以及对人类健康的风险评估提供参考。     

New model calculations of pH-depending tributyltin adsorption onto montmorillonite surface and montmorillonite-rich sediment

Interactions of the pollutant tributyltin (TBT) with mineral surfaces affects its distribution and transport in aqueous systems. In the present work, model calculations are reported that quantify TBT adsorption onto pure-phase montmorillonite (sample SWy) under various pH and salinity conditions that are important from an environmental perspective. The pH level in the system is of substantial interest because it affects the speciation of TBT in solution as well as the surface properties of the solid phase, which are both important for adsorption reactions. The model is based on the generalized diffused layer model that includes >X- sites in order to account for the cation exchange effects of TBT attraction. The presence of >AIOH and >SiOH sites atthe mineral surface was not considered separately during calculation. Instead, nonselective sites (>SOH) versus selective sites (>SsOH) were distinguished with respect to the sorptive sites on montmorillonite. The latter are characterized by a high affinity of TBT bonding. Both sorptive sites exhibit the same protolysis constants but different TBT binding constants [logK(TBT/2) = -1.18 for (>SOH), logK(TBT/1) = 3.98 for (>SsOH)]. LogK(X/TBT) for the cation exchange reaction was determined as between 3.05 and 4.14. The results indicate that the inclusion of selective sites during calculations is essential for quantifying pH-dependent TBT adsorption successfully. The parameters determined for the TBT adsorption onto pure-phase montmorillonite were subsequently used to calculate pH-dependent TBT adsorption onto a natural montmorillonite-rich sediment.     

Coupling speciation and isotope dilution techniques to study arsenic mobilization in the environment

We have developed an approach to isolate mechanisms controlling mobility and speciation of As in soil-water systems. The approach uses a combination of isotopic exchange and chromatographic/mass spectrometric As speciation techniques. We used this approach to identify mechanisms responsible for changes in the concentration of soluble As in two contaminated soils (Eaglehawk and Tavistock) subjected to different redox conditions and microbial activity. A high proportion of the total As in both soils was present in a nonlabile form. Incubation of the soils under anaerobic conditions led to changes in the concentration of soluble As in each soil but did not change the As speciation or the proportion of total As in labile forms in the soils. Hence, a decrease in soluble As in the Eaglehawk soil was the result of an Eh-induced pH decrease, enhancing the solid-phase sorption of As(V). An increase in soluble As in the Tavistock soil was due to an Eh-induced pH increase, decreasing solid-phase sorption of As(V). Incubation of the soils under aerobic conditions with microbial activity stimulated by addition of glucose resulted in no change in the solution concentration or speciation of As in the Eaglehawk soil, but led to a large increase in the concentration of soluble As in the Tavistock soil. This increase was due to conversion of exchangeable forms of As(V) into less strongly sorbed As(III) species. Incubation under anaerobic conditions in the presence of glucose resulted in a large increase in the concentration of soluble As in both soils; however, different mechanisms were found to be responsible for the increase in each soil. In the Eaglehawk soil higher concentrations of As were again due to conversion of exchangeable forms of As(V) into less strongly sorbed As(III) species. In contrast in the Tavistock soil, the increased As in solution was the result of release of As(V) from the large reservoir of nonlabile soil As.     

TBT causes regime shift in shallow lakes

Tributyltin (TBT) is an organotin compound used since the early 1960s as a biocide in boat antifouling paints. Its use has been linked to a host of negative effects in marine ecosystems including malformations and imposex in Mollusca and acute toxicity in many other aquatic animals. Yet, the consequences of TBT use in freshwaters are largely unknown. Here, for the first time we reveal that TBT may have caused hitherto unsuspected damage to freshwater ecosystems. Through an analysis of dated sediment cores collected from a system of recreationally boated, shallow lakes, we show that first evidence of TBT is associated with a dramatic loss of submerged vegetation and associated diverse animal communities. Cause and effect are difficult to unravel in our study. However, we hypothesize that TBT, through reducing populations of grazing organisms in lakes already affected by eutrophication, promoted the replacement of macrophytes by phytoplankton, ultimately leading to a regime shift in the ecosystem. Our findings may have parallels in freshwater ecosystems all over the world.     

Determination of total tin and organotin compounds in shellfish by ICP-MS

A method based on microwave digestion and inductively coupled plasma-mass spectrometric (ICP-MS) analysis was established for the determination of total tin in shellfish samples. Good linearity of the calibration curves was obtained for tin elements (r = 1.0000). Detection limit for Sn was 34.6 ng/g. Total tin concentrations in these samples ranged from non-detectable to 0.45 μg/g. High-performance liquid chromatography hyphenated with inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) was applied to the simultaneous determination of five organotin compounds in the shellfish samples. The fresh and freeze-dried shellfish samples were treated by ultrasonic extraction with two different extraction solvents. Four organotin compounds including dibutyltin (DBT), tributyltin (TBT), diphenyltin (DPhT) and triphenyltin (TPhT) in shellfish samples were detected. It was found that the dominate species in the samples were tributyltin (TBT) and triphenyltin (TPhT).     

液相色谱-电感耦合等离子体-质谱法分析海藻碘浓缩液中砷形态

目的 建立液相色谱-电感耦合等离子体质谱法(liquid chromatography-inductively coupled plasma mass spectrometry, LC-ICP-MS)测定海藻碘浓缩液中6种不同形态砷化合物的分析方法。方法 单因素实验确定对不同形态砷化合物LC-ICP-MS的分离条件, 包括流动相浓度、pH及洗脱方式。以总砷提取效率的高低评价三种不同的提取砷化合物的方法, 确定最佳方法。结果 以稀硝酸浸提的前处理方法的提取效果最佳, 提取效率为84.28%~92.99%;以25 mmol/L pH8.0磷酸二氢铵溶液和水作为流动相, 采用梯度洗脱的方式, 可以将6种砷形态完全分离,结果显示6种海藻碘样品中砷甜菜碱AsB含量较多, 而亚砷酸盐As(III)、砷酸盐As(V)和二甲基砷酸DMA含量较少, 未检测出砷胆碱AsC和一甲基砷酸MMA, 样品有毒砷含量占浓缩液总砷含量的2.01%~3.69%, 本方法加标回收率在80.4%~101.5%之间。结论 海藻碘浓缩液中砷形态的主要存在形式为AsB,本方法准确、简单,适合海藻碘浓缩液中砷形态分析。     

Speciation and release kinetics of zinc in contaminated paddy soils

Zinc is an important nutrient for plants, but it can be toxic at high concentrations. The solubility and speciation of Zn is controlled by many factors, especially soil pH and Eh, which can vary in lowland rice culture. This study determined Zn speciation and release kinetics in Cd-Zn cocontaminated alkaline and acidified paddy soils, under various flooding periods and draining conditions, by employing synchrotron-based techniques and a stirred-flow kinetic method. Results showed almost no change in Zn speciation and release kinetics in the two soils, although the soils were subjected to different flooding periods and draining conditions. The mineral phases in which Zn is immobilized in the soil samples were constrained by linear least squares fitting (LLSF) analyses of bulk X-ray absorption fine structure (XAFS) spectra. Only two main phases were identified by LLSF, i.e., Zn-layered double hydroxides (Zn/Mg-hydrotalcite-like, and ZnAl-LDH) and Zn-phyllosilicates (Zn-kerolite). Under all soil pHs, flooding, and draining conditions, less than 22% of Zn was desorbed from the soil after a two-hour desorption experiment. The information on Zn chemistry obtained in this study will be useful in finding the best strategy to control Cd and Zn bioavailability in the Cd-Zn cocontaminated paddy soils.     

Time-dependent changes of zinc speciation in four soils contaminated with zincite or sphalerite

The long-term speciation of Zn in contaminated soils is strongly influenced by soil pH, clay, and organic matter content as well as Zn loading. In addition, the type of Zn-bearing contaminant entering the soil may influence the subsequent formation of pedogenic Zn species, but systematic studies on such effects are currently lacking. We therefore conducted a soil incubation study in which four soils, ranging from strongly acidic to calcareous, were spiked with 2000 mg/kg Zn using either ZnO (zincite) or ZnS (sphalerite) as the contamination source. The soils were incubated under aerated conditions in moist state for up to four years. The extractability and speciation of Zn were assessed after one, two, and four years using extractions with 0.01 M CaCl(2) and Zn K-edge X-ray absorption fine structure (XAFS) spectroscopy, respectively. After four years, more than 90% of the added ZnO were dissolved in all soils, with the fastest dissolution occurring in the acidic soils. Contamination with ZnO favored the formation of Zn-bearing layered double hydroxides (LDH), even in acidic soils, and to a lesser degree Zn-phyllosilicates and adsorbed Zn species. This was explained by locally elevated pH and high Zn concentrations around dissolving ZnO particles. Except for the calcareous soil, ZnS dissolved more slowly than ZnO, reaching only 26 to 75% of the added ZnS after four years. ZnS dissolved more slowly in the two acidic soils than in the near-neutral and the calcareous soil. Also, the resulting Zn speciation was markedly different between these two pairs of soils: Whereas Zn bound to hydroxy-interlayered clay minerals (HIM) and octahedrally coordinated Zn sorption complexes prevailed in the two acidic soils, Zn speciation in the neutral and the calcareous soil was dominated by Zn-LDH and tetrahedrally coordinated inner-sphere Zn complexes. Our results show that the type of Zn-bearing contaminant phase can have a significant influence on the formation of pedogenic Zn species in soils. Important factors include the rate of Zn release from the contaminant phases and effects of the contaminant phase on bulk soil properties and on local chemical conditions around weathering contaminant particles.     

Determination of tributyltin through ultrasonic assisted micelle mediated extraction and GFAAS: Application to the monitoring of tributyltin levels in Greek marine species

Ultrasonically assisted extraction into the micelles of both non-ionic and anionic surfactants was applied as a methodology for the isolation of tributyltin (TBT) from fish and mussel tissue prior to determination with graphite furnace atomic absorption spectrometry (GFAAS). The proposed methodology includes extraction of organotin species in the micelles of Triton X-114 or Sodium Dodecane Sulphonic Acid (SDSA), accelerated by the application of ultrasounds. Isolation and subsequent determination of TBT is achieved by ultrasonic assisted back extraction into a water immiscible solvent, utilising the selective partition of TBT from an alkaline environment. Quantitation is performed by GFAAS. Seventy-seven seafood samples including sardines, anchovies and mussels were analysed for tributyltin (TBT) from different coastal regions of northern, eastern and western Greece on the Aegean and the Ionian Sea. Results showed that the shellfish contained a higher amount of TBT than fish (mean value of 0.91 μg/kg for fish and 2.21 μg/kg for mussels). The highest TBT concentration recorded was 19.50 μg/kg for sardines in N. Mihaniona and 14.27 μg/kg for mussels in Fthiotida. TBT concentrations found in the present study were much lower than those reported in the literature regarding Greece and other countries.     

Selenium in cereals: Insight into species of the element from total amount

Selenium (Se) is a trace mineral micronutrient essential for human health. The diet is the main source of Se intake. Se-deficiency is associated with many diseases, and up to 1 billion people suffer from Se-deficiency worldwide. Cereals are considered a good choice for Se intake due to their daily consumption as staple foods. Much attention has been paid to the contents of Se in cereals and other foods. Se-enriched cereals are produced by biofortification. Notably, the gap between the nutritional and toxic levels of Se is fairly narrow. The chemical structures of Se compounds, rather than their total contents, contribute to the bioavailability, bioactivity, and toxicity of Se. Organic Se species show better bioavailability, higher nutritional value, and less toxicity than inorganic species. In this paper, we reviewed the total content of Se in cereals, Se speciation methods, and the biological effects of Se species on human health. Selenomethionine (SeMet) is generally the most prevalent and important Se species in cereal grains. In conclusion, Se species should be considered in addition to the total Se content when evaluating the nutritional and toxic values of foods such as cereals.     

X-ray absorption spectroscopy study of the effects of pH and ionic strength on Pb(II) sorption to amorphous silica

Pb(III) sorption to hydrous amorphous SiO2 was studied as a function of pH and ionic strength using XAS to characterize the sorption products formed. Pb sorption increased with increasing pH and decreasing ionic strength. The XAS data indicated that the mechanism of Pb(II) sorption to the SiO2 surface was pH-dependent. At pH < 4.5, a mononuclear inner-sphere Pb sorption complex with ionic character dominated the Pb surface speciation. Between pH 4.5 and pH 5.6, sorption increasingly occurred via the formation of surface-attached covalent polynuclear Pb species, possibly Pb-Pb dimers, and these were the dominant Pb complexes at pH > or = 6.3. Decreasing ionic strength from I = 0.1 to I = 0.005 M NaClO4 significantly increased Pb sorption but did not strongly influence the average local coordination environment of sorbed Pb at given pH, suggesting that the formation of mononuclear and polynuclear Pb complexes at the surface were coupled; possibly, Pb monomers control the formation of Pb polynuclear species by diffusion along the surface, or they act as nucleation centers for additional Pb uptake from solution. This study shows that the effectiveness of SiO2 in retaining Pb(II) is strongly dependent on solution conditions. At low pH, Pb(II) may be effectively remobilized by competition with other cations, whereas sorbed Pb is expected to become less susceptible to desorption with increasing pH. However, unlike for Ni(II) and Co(II), no lead phyllosilicates are formed at these higher pH values; therefore, SiO2 is expected to be a less effective sink for Pb immobilization than for these other metals.