Rapid Analysis of the Size Distribution of Metal-Containing Aerosol.

Conventional methods to measure the metallic content of particles by size are time consuming and expensive, requiring collection of particles with a cascade impactor and subsequent metals analysis by inductively coupled plasma mass spectrometry (ICP-MS). In this work, we describe a rapid way to measure the size distribution of metal-containing particles from 10 nm to 20 µm, using a nano micro-orifice uniform-deposit impactor (nano-MOUDI) to size-selective and collect particles that are then analyzed with a field portable X-ray fluorescence (FP-XRF) to determine metal composition and concentration. The nano-MOUDI was used to sample a stainless-steel aerosol produced by a spark discharge system. The particle-laden substrates were then analyzed directly with FP-XRF and then with ICP-MS. Results from FP-XRF were linearly correlated with results from ICP-MS (R2 = 0.91 for Fe and R2 = 0.84 for Cr). Although the FP-XRF was unable to detect Fe particles at mass per substrate loadings less than 2.5 µg effectively, it produced results similar to those using the ICP-MS at a mass per substrate loading greater than 2.5 µg.

Effects of Coal Fly Ash Particulate Matter on the Antimicrobial Activity of Airway Surface Liquid.

BACKGROUND: Sustained exposure to ambient particulate matter (PM) is a global cause of mortality. Coal fly ash (CFA) is a byproduct of coal combustion and is a source of anthropogenic PM with worldwide health relevance. The airway epithelia are lined with fluid called airway surface liquid (ASL), which contains antimicrobial proteins and peptides (AMPs). Cationic AMPs bind negatively charged bacteria to exert their antimicrobial activity. PM arriving in the airways could potentially interact with AMPs in the ASL to affect their antimicrobial activity. OBJECTIVES: We hypothesized that PM can interact with ASL AMPs to impair their antimicrobial activity. METHODS: We exposed pig and human airway explants, pig and human ASL, and the human cationic AMPs ß-defensin-3, LL-37, and lysozyme to CFA or control. Thereafter, we assessed the antimicrobial activity of exposed airway samples using both bioluminescence and standard colony-forming unit assays. We investigated PM-AMP electrostatic interaction by attenuated total reflection Fourier-transform infrared spectroscopy and measuring the zeta potential. We also studied the adsorption of AMPs on PM. RESULTS: We found increased bacterial survival in CFA-exposed airway explants, ASL, and AMPs. In addition, we report that PM with a negative surface charge can adsorb cationic AMPs and form negative particle-protein complexes. CONCLUSION: We propose that when CFA arrives at the airway, it rapidly adsorbs AMPs and creates negative complexes, thereby decreasing the functional amount of AMPs capable of killing pathogens. These results provide a novel translational insight into an early mechanism for how ambient PM increases the susceptibility of the airways to bacterial infection. https://doi.org/10.1289/EHP876.

Nonwoven textile for use in a nanoparticle respiratory deposition sampler.

The nanoparticle respiratory deposition (NRD) sampler is a personal sampler that combines a cyclone, impactor, and a nylon mesh diffusion stage to measure a worker's exposure to nanoparticles. The concentration of titanium in the nylon mesh of the diffusion stage complicates the application of the NRD sampler for assessing exposures to titanium dioxide nanoparticles. This study evaluated commercially available nonwoven textiles for use as an alternative media in the diffusion stage of the NRD sampler. Three textiles were selected as containing little titanium from an initial screening of 11 textiles by field portable x-ray fluorescence (FPXRF). Further evaluation on these three textiles was conducted to determine the concentration of titanium and other metals by inductively coupled plasma-optical emission spectroscopy (ICP-OES), the number of layers required to achieve desired collection characteristics for use as the diffusion stage in the NRD sampler (i.e., the nanoparticulate matter, NPM, criterion), and the pressure drop associated with that number of layers. Only three (two composed of cotton fibers, C1 and C2; and one of viscose bamboo and cotton fibers, BC) of 11 textiles screened had titanium concentrations below the limit of detection the XRF device (0.15 µg/cm2). Multiple metals, including small amounts of titanium, were found in each of the three nonwoven textiles using ICP-OES. The number of 25-mm-diameter layers required to achieve the collection efficiency by size required for the NRD sampler was three for C1 (R2 = 0.95 with reference to the NPM criterion), two for C2 (R2 = 0.79), and three for BC (R2 = 0.87). All measured pressure drops were less than theoretical and even the greatest pressure drop of 65.4 Pa indicated that a typical personal sampling pump could accommodate any of the three nonwoven textiles in the NRD sampler. The titanium concentration, collection efficiency, and measured pressure drops show there is a potential for nonwoven textiles to be used as the diffusion stage of the NRD sampler.

Size-dependent cytotoxicity of copper oxide nanoparticles in lung epithelial cells.

The increasing use of copper oxide (CuO) nanoparticles (NPs) in medicine and industry demands an understanding of their potential toxicities. In this study, we compared the in vitro cytotoxicity of CuO NPs of two distinct sizes (4 and 24 nm) using the A549 human lung cell line. Despite possessing similar surface and core oxide compositions, 24 nm CuO NPs were significantly more cytotoxic than 4 nm CuO NPs. The difference in size may have affected the rate of entry of NPs into the cell, potentially influencing the amount of intracellular dissolution of Cu2+ and causing a differential impact on cytotoxicity.

Reduction of Biomechanical and Welding Fume Exposures in Stud Welding.

The welding of shear stud connectors to structural steel in construction requires a prolonged stooped posture that exposes ironworkers to biomechanical and welding fume hazards. In this study, biomechanical and welding fume exposures during stud welding using conventional methods were compared to exposures associated with use of a prototype system that allowed participants to weld from an upright position. The effect of base material (i.e. bare structural beam versus galvanized decking) on welding fume concentration (particle number and mass), particle size distribution, and particle composition was also explored. Thirty participants completed a series of stud welding simulations in a local apprenticeship training facility. Use of the upright system was associated with substantial reductions in trunk inclination and the activity levels of several muscle groups. Inhalable mass concentrations of welding fume (averaged over ~18 min) when using conventional methods were high (18.2 mg m(-3) for bare beam; 65.7 mg m(-3) for through deck), with estimated mass concentrations of iron (7.8 mg m(-3) for bare beam; 15.8 mg m(-3) for through deck), zinc (0.2 mg m(-3) for bare beam; 15.8 mg m(-3) for through deck), and manganese (0.9 mg m(-3) for bare beam; 1.5 mg m(-3) for through deck) often exceeding the American Conference of Governmental Industrial Hygienists Threshold Limit Values (TLVs). Number and mass concentrations were substantially reduced when using the upright system, although the total inhalable mass concentration remained above the TLV when welding through decking. The average diameters of the welding fume particles for both bare beam (31±17 nm) through deck conditions (34±34 nm) and the chemical composition of the particles indicated the presence of metallic nanoparticles. Stud welding exposes ironworkers to potentially high levels of biomechanical loading (primarily to the low back) and welding fume. The upright system used in this study improved exposure levels during stud welding simulations, but further development is needed before field deployment is possible.

Nano-Bio Interactions of Porous and Nonporous Silica Nanoparticles of Varied Surface Chemistry: A Structural, Kinetic, and Thermodynamic Study of Protein Adsorption from RPMI Culture Medium.

Understanding complex chemical changes that take place at nano-bio interfaces is of great concern for being able to sustainably implement nanomaterials in key applications such as drug delivery, imaging, and environmental remediation. Typical in vitro assays use cell viability as a proxy to understanding nanotoxicity but often neglect how the nanomaterial surface can be altered by adsorption of solution-phase components in the medium. Protein coronas form on the nanomaterial surface when incubated in proteinaceous solutions. Herein, we apply a broad array of techniques to characterize and quantify protein corona formation on silica nanoparticle surfaces. The porosity and surface chemistry of the silica nanoparticles have been systematically varied. Using spectroscopic tools such as FTIR and circular dichroism, structural changes and kinetic processes involved in protein adsorption were evaluated. Additionally, by implementing thermogravimetric analysis, quantitative protein adsorption measurements allowed for the direct comparison between samples. Taken together, these measurements enabled the extraction of useful chemical information on protein binding onto nanoparticles in solution. Overall, we demonstrate that small alkylamines can increase protein adsorption and that even large polymeric molecules such as poly(ethylene glycol) (PEG) cannot prevent protein adsorption in these systems. The implications of these results as they relate to further understanding nano-bio interactions are discussed.

Accurate quantification of tio2 nanoparticles collected on air filters using a microwave-assisted acid digestion method.

Titanium dioxide (TiO(2)) particles, including nanoparticles with diameters smaller than 100 nm, are used extensively in consumer products. In a 2011 current intelligence bulletin, the National Institute of Occupational Safety and Health (NIOSH) recommended methods to assess worker exposures to fine and ultrafine TiO(2) particles and associated occupational exposure limits for these particles. However, there are several challenges and problems encountered with these recommended exposure assessment methods involving the accurate quantitation of titanium dioxide collected on air filters using acid digestion followed by inductively coupled plasma optical emission spectroscopy (ICP-OES). Specifically, recommended digestion methods include the use of chemicals, such as perchloric acid, which are typically unavailable in most accredited industrial hygiene laboratories due to highly corrosive and oxidizing properties. Other alternative methods that are used typically involve the use of nitric acid or combination of nitric acid and sulfuric acid, which yield very poor recoveries for titanium dioxide. Therefore, given the current state of the science, it is clear that a new method is needed for exposure assessment. In this current study, a microwave-assisted acid digestion method has been specifically designed to improve the recovery of titanium in TiO(2) nanoparticles for quantitative analysis using ICP-OES. The optimum digestion conditions were determined by changing several variables including the acids used, digestion time, and temperature. Consequently, the optimized digestion temperature of 210°C with concentrated sulfuric and nitric acid (2:1 v/v) resulted in a recovery of >90% for TiO(2). The method is expected to provide for a more accurate quantification of airborne TiO(2) particles in the workplace environment.

Porous Polyurethane Foam for Use as a Particle Collection Substrate in a Nanoparticle Respiratory Deposition Sampler.

Porous polyurethane foam was evaluated to replace the eight nylon meshes used as a substrate to collect nanoparticles in the Nanoparticle Respiratory Deposition (NRD) sampler. Cylindrical (25-mm diameter by 40-mm deep) foam with 110 pores per inch was housed in a 25-mm-diameter conductive polypropylene cassette cowl compatible with the NRD sampler. Pristine foam and nylon meshes were evaluated for metals content via elemental analysis. The size-selective collection efficiency of the foam was evaluated using salt (NaCl) and metal fume aerosols in independent tests. Collection efficiencies were compared to the nanoparticulate matter (NPM) criterion and a semi-empirical model for foam. Changes in collection efficiency and pressure drop of the foam and nylon meshes were measured after loading with metal fume particles as measures of substrate performance. Substantially less titanium was found in the foam (0.173 µg sampler-1) compared to the nylon mesh (125 µg sampler-1), improving the detection capabilities of the NRD sampler for titanium dioxide particles. The foam collection efficiency was similar to that of the nylon meshes and the NPM criterion (R2 = 0.98, for NaCl), although the semi-empirical model underestimated the experimental efficiency (R2 = 0.38). The pressure drop across the foam was 8% that of the nylon meshes when pristine and changed minimally with metal fume loading (~ 19 mg). In contrast, the pores of the nylon meshes clogged after loading with ~ 1 mg metal fume. These results indicate that foam is a suitable substrate to collect metal (except for cadmium) nanoparticles in the NRD sampler.

A Granular Bed for Use in a Nanoparticle Respiratory Deposition Sampler.

A granular bed was designed to collect nanoparticles as an alternative to nylon mesh screens for use in a nanoparticle respiratory deposition (NRD) sampler. The granular bed consisted of five layers in series: a coarse mesh, a large-bead layer, a small-bead layer, a second large-bead layer, and a second coarse mesh. The bed was designed to primarily collect particles in the small-bead layer, with the coarse mesh and large-bead layers designed to hold the collection layer in position. The collection efficiency of the granular bed was measured for varying depths of the small-bead layer and for test particles with different shape (cuboid, salt particles; and fractal, and stainless steel and welding particles). Experimental measurements of collection efficiency were compared to estimates of efficiency from theory and to the nanoparticulate matter (NPM) criterion, which was established to reflect the total deposition in the human respiratory system for particles smaller than 300 nm. The shape of the collection efficiency curve for the granular bed was similar to the NPM criterion in these experiments. The collection efficiency increased with increasing depth of the small-bead layer: the particle size associated with 50% collection efficiency, d50, for salt particles was 25 nm for a depth of 2.2 mm, 35 nm for 3.2 mm, and 45 nm for 4.3 mm. The best-fit to the NPM criterion was found for the bed with a small-bead layer of 3.2 mm. Compared to cubic salt particles, the collection efficiency was higher for fractal-shaped particles larger than 50 nm, presumably due to increased interception.

Iron oxide nanoparticles induce Pseudomonas aeruginosa growth, induce biofilm formation, and inhibit antimicrobial peptide function.

Given the increased use of iron-containing nanoparticles in a number of applications, it is important to understand any effects that iron-containing nanoparticles can have on the environment and human health. Since iron concentrations are extremely low in body fluids, there is potential that iron-containing nanoparticles may influence the ability of bacteria to scavenge iron for growth, affect virulence and inhibit antimicrobial peptide (AMP) function. In this study, Pseudomonas aeruginosa (PA01) and AMPs were exposed to iron oxide nanoparticles, hematite (α-Fe2O3), of different sizes ranging from 2 to 540 nm (2 ± 1, 43 ± 6, 85 ± 25 and 540 ± 90 nm) in diameter. Here we show that the greatest effect on bacterial growth, biofilm formation, and AMP function impairment is found when exposed to the smallest particles. These results are attributed in large part to enhanced dissolution observed for the smallest particles and an increase in the amount of bioavailable iron. Furthermore, AMP function can be additionally impaired by adsorption onto nanoparticle surfaces. In particular, lysozyme readily adsorbs onto the nanoparticle surface which can lead to loss of peptide activity. Thus, this current study shows that co-exposure of nanoparticles and known pathogens can impact host innate immunity. Therefore, it is important that future studies be designed to further understand these types of impacts.

Physicochemical Characterization of Simulated Welding Fume from a Spark Discharge System.

This study introduces spark discharge system (SDS) as a way to simulate welding fumes. The SDS was developed using welding rods as electrodes with an optional coagulation chamber. The size, morphology, composition, and concentration of the fume produced and the concentration of ozone (O3) and nitrogen oxides (NOX) were characterized. The number median diameter (NMD) and total number concentration (TNC) of fresh fume particles were ranged 10-23 nm and 3.1×107-6×107 particles/cm3, respectively. For fresh fume particles, the total mass concentration (TMC) measured gravimetrically ranged 85-760 µg/m3. The size distribution was stable over a period of 12 h. The NMD and TNC of aged fume particles were ranged 81-154 nm and 1.5×106-2.7×106 particles/cm3, respectively. The composition of the aged fume particles was dominated by Fe and O with an estimated stoichiometry between that of Fe2O3 and Fe3O4. Concentrations of O3 and NOX were ranged 0.07-2.2 ppm and 1-20 ppm, respectively. These results indicate that the SDS is capable of producing stable fumes over a long-period that are similar to actual welding fumes. This system may be useful in toxicological studies and evaluation of instrumentation.

Histidine adsorption on TiO2 nanoparticles: an integrated spectroscopic, thermodynamic, and molecular-based approach toward understanding nano-bio interactions.

Nanoparticles in biological media form dynamic entities as a result of competitive adsorption of proteins on nanoparticle surfaces called protein coronas. The protein affinity toward nanoparticle surfaces potentially depends on the constituent amino acid side chains which are on the protein exterior and thus exposed to the solution and available for interaction. Therefore, studying the adsorption of individual amino acids on nanoparticle surfaces can provide valuable insights into the overall evolution of nanoparticles in solution and the protein corona that forms. In the current study, the surface adsorption of l-histidine on TiO2 nanoparticles with a diameter of 5 nm at pH 7.4 (physiological pH) is studied from both macroscopic and molecular perspectives. Quantitative adsorption measurements of l-histidine on 5 nm TiO2 particles yield maximum adsorption coverage of 6.2 ± 0.3 × 10(13) molecules cm(-2) at 293 K and pH 7.4. These quantitative adsorption measurements also yield values for the equilibrium constant and free energy of adsorption of K = 4.3 ± 0.5 × 10(2) L mol(-1) and ΔG = -14.8 ± 0.3 kJ mol(-1), respectively. Detailed analysis of the adsorption between histidine and 5 nm TiO2 nanoparticle surfaces with attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy indicates both the imidazole side chain and the amine group interacting with the nanoparticle surface and the adsorption to be reversible. The adsorption results in no change in surface charge and therefore does not change nanoparticle-nanoparticle interactions and thus aggregation behavior of these 5 nm TiO2 nanoparticles in aqueous solution.

ATR-FTIR spectroscopy as a tool to probe surface adsorption on nanoparticles at the liquid-solid interface in environmentally and biologically relevant media.

Given the importance of nanoparticle surface composition in nanotoxicology, analytical tools that can probe nanoparticle surfaces in aqueous media are crucial but remain limited. Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy is a technique capable of in situ characterization of the liquid-solid interface to probe surface adsorption on nanoparticle surfaces in environmentally and biologically relevant media. Furthermore, given that the interfacial region in these media is dynamic, ATR-FTIR spectroscopy facilitates monitoring these dynamics by interrogating a layer of immobilized nanoparticles coated on the ATR element while changing the overlying aqueous phase. The molecular information acquired from this technique allows for the determination of the adsorption mode, including conformational and structural changes of the coordinating ligand, and can directly measure ligand displacement reactions. Furthermore, in some cases, ATR-FTIR spectroscopy can be used as a quantitative surface analytical tool. In this article, we briefly review the fundamentals of the technique and then provide several examples of using ATR-FTIR spectroscopy to probe nanoparticle surfaces in general with respect to: (i) the adsorption of different environmentally and biologically relevant coordinating ligands; (ii) competitive ligand adsorption and; (iii) the determination of kinetic and thermodynamic parameters. We have also investigated surface adsorption of TiO2 nanoparticles in different biological media typically used for toxicity studies and show that the surface composition of TiO2 nanoparticles depends to a large extent on the composition of the medium due to surface adsorption. This result has important implications for the interpretation of toxicity data as well as inter-comparisons between toxicity studies.

Chitosan coating of copper nanoparticles reduces in vitro toxicity and increases inflammation in the lung.

Despite their potential for a variety of applications, copper nanoparticles induce very strong inflammatory responses and cellular toxicity following aerosolized delivery. Coating metallic nanoparticles with polysaccharides, such as biocompatible and antimicrobial chitosan, has the potential to reduce this toxicity. In this study, copper nanoparticles were coated with chitosan using a newly developed and facile method. The presence of coating was confirmed using x-ray photoelectron spectroscopy, rhodamine tagging of chitosan followed by confocal fluorescence imaging of coated particles and observed increases in particle size and zeta potential. Further physical and chemical characteristics were evaluated using dissolution and x-ray diffraction studies. The chitosan coating was shown to significantly reduce the toxicity of copper nanoparticles after 24 and 52 h and the generation of reactive oxygen species as assayed by DHE oxidation after 24 h in vitro. Conversely, inflammatory response, measured using the number of white blood cells, total protein, and cytokines/chemokines in the bronchoalveolar fluid of mice exposed to chitosan coated versus uncoated copper nanoparticles, was shown to increase, as was the concentration of copper ions. These results suggest that coating metal nanoparticles with mucoadhesive polysaccharides (e.g. chitosan) could increase their potential for use in controlled release of copper ions to cells, but will result in a higher inflammatory response if administered via the lung.

Environmental implications of nanoparticle aging in the processing and fate of copper-based nanomaterials.

Copper nanomaterials are being used in a large number of commercial products because these materials exhibit unique optical, magnetic, and electronic properties. Metallic copper nanoparticles, which often have a thin surface oxide layer, can age in the ambient environment and become even more oxidized over time. These aged nanoparticles will then have different properties compared to the original nanoparticles. In this study, we have characterized three different types of copper-based nanoparticle (NP) samples designated as Cu(new) NPs, Cu(aged) NPs, and CuO NPs that differ in the level of oxidation. The solution phase behavior of these three copper-based nanoparticle samples is investigated as a function of pH and in the presence and absence of two common, complexing organic acids, citric and oxalic acid. The behavior of these three copper-based NP types shows interesting differences. In particular, Cu(aged) NPs exhibit unique chemistry including oxide phases that form and surface adsorption properties. Overall, the current study provides some insights into the impacts of nanoparticle aging and how the physicochemical characteristics and reactivity of nanomaterials can change upon aging.

Dissolution of ZnO nanoparticles at circumneutral pH: a study of size effects in the presence and absence of citric acid.

Understanding size-dependent processes, including dissolution, of engineered nanoparticles is essential in addressing the potential environmental and health impacts of these materials as well as their long-term stability. In this study, experimental measurements of size-dependent dissolution of well-characterized zinc oxide (ZnO) nanoparticles with particle diameters in the range of 4 to 130 nm have been measured at circumneutral pH (pH 7.5) and compared. Dissolution was found to be enhanced with smaller ZnO nanoparticles compared to larger-sized particles, even though the nanoparticles were present in solution as aggregates with hydrodynamic diameters on the order of 1-3 µm in size. The presence of citric acid significantly enhanced the extent of ZnO dissolution for all sizes, and the greatest enhancement was observed for the 4 nm particles. Although these results are found to be in qualitative agreement with theoretical predictions, a linearized form of the Kelvin equation to calculate a surface free energy yielded quantities inconsistent with expected values from the literature. Reasons for this inconsistency are discussed and include potential deviations of solubility behavior from classical thermodynamics as a result of a lack of detailed knowledge of surface structure and surface properties, including the presence of different surface crystal facets, and the aggregation state.

The devil is in the details (or the surface): impact of surface structure and surface energetics on understanding the behavior of nanomaterials in the environment.

Metal and metal oxide nanomaterials are found in many consumer products for use in a wide range of applications including catalysis, sensors and contaminant remediation. Because of the extensive use of metal-based nanomaterials, there are concerns that these materials have the potential to get into the environment sometime during production, distribution, use and/or disposal. In particular, there exists the potential that they will make their way into water systems, e.g. drinking water systems, ground water systems, estuaries and lakes. In this review, some of the uncertainties in understanding nanoparticle behavior, which is often due to a lack of fundamental knowledge of the surface structure and surface energetics for very small particles, are discussed. Although classical models may provide guidance for understanding dissolution and aggregation of nanoparticles in water, it is the detailed surface structure and surface chemistry that are needed to accurately describe the surface free energy, a large component of the total free energy, in order to fully understand these processes. Without this information, it is difficult to develop a conceptual framework for understanding the fate, transport and potential toxicity of nanomaterials. Needed research areas to fill this void are discussed.

Aggregation and dissolution of 4 nm ZnO nanoparticles in aqueous environments: influence of pH, ionic strength, size, and adsorption of humic acid.

Metal oxide nanoparticles are used in a wide range of commercial products, leading to an increased interest in the behavior of these materials in the aquatic environment. The current study focuses on the stability of some of the smallest ZnO nanomaterials, 4 ± 1 nm in diameter nanoparticles, in aqueous solutions as a function of pH and ionic strength as well as upon the adsorption of humic acid. Measurements of nanoparticle aggregation due to attractive particle-particle interactions show that ionic strength, pH, and adsorption of humic acid affect the aggregation of ZnO nanoparticles in aqueous solutions, which are consistent with the trends expected from Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Measurements of nanoparticle dissolution at both low and high pH show that zinc ions can be released into the aqueous phase and that humic acid under certain, but not all, conditions can increase Zn(2+)(aq) concentrations. Comparison of the dissolution of ZnO nanoparticles of different nanoparticle diameters, including those near 15 and 240 nm, shows that the smallest nanoparticles dissolve more readily. Although qualitatively this enhancement in dissolution can be predicted by classical thermodynamics, quantitatively it does not describe the dissolution behavior very well.

Citric acid adsorption on TiO2 nanoparticles in aqueous suspensions at acidic and circumneutral pH: surface coverage, surface speciation, and its impact on nanoparticle-nanoparticle interactions.

Citric acid plays an important role as a stabilizer in several nanomaterial syntheses and is a common organic acid found in nature. Here, the adsorption of citric acid onto TiO(2) anatase nanoparticles with a particle diameter of ca. 4 nm is investigated at circumneutral and acidic pHs. This study focuses on both the details of the surface chemistry of citric acid on TiO(2), including measurements of surface coverage and speciation, and its impact on nanoparticle behavior. Using macroscopic and molecular-based probes, citric acid adsorption and nanoparticle interactions are measured with quantitative solution phase adsorption measurements, attenuated total reflection-FTIR spectroscopy, dynamic light scattering techniques, and zeta-potential measurements as a function of solution pH. The results show that surface coverage is a function of pH and decreases with increasing pH. Surface speciation differs from the bulk solution and is time dependent. After equilibration, the fully deprotonated citrate ion is present on the surface regardless of the highly acidic solution pH indicating pK(a) values of surface adsorbed species are lower than those in solution. Nanoparticle interactions are also probed through measurements of aggregation and the data show that these interactions are complex and depend on the detailed interplay between bulk solution pH and surface chemistry.