Unveiling the effects of protein corona formation on the aggregation kinetics of gold nanoparticles in monovalent and divalent electrolytes.

Elucidation of the aggregation behaviors of gold nanoparticles (AuNPs) in water systems is crucial to understanding their environmental fate and transport as well as human health effects. We investigated the early-stage aggregation kinetics of AuNPs coated by human serum albumin (HSA) protein corona (PC) in NaCl and CaCl2 through time-resolved dynamic light scattering. We found that the aggregation of PC-AuNPs depended on the concerted effects of electrolyte concentration, valence, and HSA concentration. At low HSA concentration (≤0.005 g/L), the aggregation kinetics of PC-AuNPs was similar to that of bare AuNPs due to insignificant HSA adsorption. At intermediate HSA concentrations of 0.025-0.050 g/L, the aggregation of PC-AuNPs was retarded in both electrolytes due to steric repulsive forces imparted by the PCs. Additionally, HSA PCs had a weaker retardation effect on PC-AuNPs aggregation in divalent than in monovalent electrolytes. Quartz crystal microbalance measurements revealed that the presence of Ca2+ promoted additional HSA adsorption on PC-AuNPs likely via -COO-Ca2+ bond, and eventually enhanced the aggregation between PC-AuNPs. High-concentration HSA (>0.5 g/L) resulted in no PC-AuNPs aggregation regardless of electrolyte valence and concentrations. Finally, desorption of HSA barely occurred after adsorption on the gold surface, suggesting that the formation of PC-AuNPs is mostly irreversible.

Advancing Global Health Surveillance of Mycotoxin Exposures using Minimally Invasive Sampling Techniques: A State-of-the-Science Review.

Mycotoxins are a heterogeneous group of toxins produced by fungi that can grow in staple crops (e.g., maize, cereals), resulting in health risks due to widespread exposure from human consumption and inhalation. Dried blood spot (DBS), dried serum spot (DSS), and volumetric tip microsampling (VTS) assays were developed and validated for several important mycotoxins. This review summarizes studies that have developed these assays to monitor mycotoxin exposures in human biological samples and highlights future directions to facilitate minimally invasive sampling techniques as global public health tools. A systematic search of PubMed (MEDLINE), Embase (Elsevier), and CINAHL (EBSCO) was conducted. Key assay performance metrics were extracted to provide a critical review of the available methods. This search identified 11 published reports related to measuring mycotoxins (ochratoxins, aflatoxins, and fumonisins) using DBS/DSS and VTS assays. Multimycotoxin assays adapted for DBS/DSS and VTS have undergone sufficient laboratory validation for applications in large-scale population health and human biomonitoring studies. Future work should expand the number of mycotoxins that can be measured in multimycotoxin assays, continue to improve multimycotoxin assay sensitivities of several biomarkers with low detection rates, and validate multimycotoxin assays across diverse populations with varying exposure levels. Validated low-cost and ultrasensitive minimally invasive sampling methods should be deployed in human biomonitoring and public health surveillance studies to guide policy interventions to reduce inequities in global mycotoxin exposures.

A state-of-the-science review and guide for measuring environmental exposure biomarkers in dried blood spots.

BACKGROUND: Dried blood spot (DBS) sampling is a simple, cost-effective, and minimally invasive alternative to venipuncture for measuring exposure biomarkers in public health and epidemiological research. DBS sampling provides advantages in field-based studies conducted in low-resource settings and in studies involving infants and children. In addition, DBS samples are routinely collected from newborns after birth (i.e., newborn dried blood spots, NDBS), with many states in the United States permitting access to archived NDBS samples for research purposes. OBJECTIVES: We review the state of the science for analyzing exposure biomarkers in DBS samples, both archived and newly collected, and provide guidance on sample collection, storage, and blood volume requirements associated with individual DBS assays. We discuss recent progress regarding analytical methods, analytical sensitivity, and specificity, sample volume requirements, contamination considerations, estimating extracted blood volumes, assessing stability and analyte recovery, and hematocrit effects. METHODS: A systematic search of PubMed (MEDLINE), Embase (Elsevier), and CINAHL (EBSCO) was conducted in March 2022. DBS method development and application studies were divided into three main chemical classes: environmental tobacco smoke, trace elements (including lead, mercury, cadmium, and arsenic), and industrial chemicals (including endocrine-disrupting chemicals and persistent organic pollutants). DBS method development and validation studies were scored on key quality-control and performance parameters by two members of the review team. RESULTS: Our search identified 47 published reports related to measuring environmental exposure biomarkers in human DBS samples. A total of 28 reports (37 total studies) were on methods development and validation and 19 reports were primarily the application of previously developed DBS assays. High-performing DBS methods have been developed, validated, and applied for detecting environmental exposures to tobacco smoke, trace elements, and several important endocrine-disrupting chemicals and persistent organic pollutants. Additional work is needed for measuring cadmium, arsenic, inorganic mercury, and bisphenol A in DBS and NDBS samples. SIGNIFICANCE: We present an inventory and critical review of available assays for measuring environmental exposure biomarkers in DBS and NDBS samples to help facilitate this sampling medium as an emerging tool for public health (e.g., screening programs, temporal biomonitoring) and environmental epidemiology (e.g., field-based studies).

An Ovarian Steroid Metabolomic Pathway Analysis in Basal and Polycystic Ovary Syndrome (PCOS)-like Gonadotropin Conditions Reveals a Hyperandrogenic Phenotype Measured by Mass Spectrometry.

Prior work has demonstrated that murine ovarian explants and isolated ovarian follicles can recapitulate human-like 28-day cycles in vitro with normal patterns of estradiol and progesterone secretion in response to gonadotropin stimulation. The objective of this study was to manipulate the gonadotropin stimulation protocol to mimic polycystic ovary syndrome (PCOS) and assess the resulting changes in ovarian steroidogenesis. A secondary aim of the study was to develop a high-throughput, sensitive, and specific liquid chromatography with tandem mass spectrometry (LC-MS/MS) assay to measure seven steroid hormones (estrone, estradiol, progesterone, testosterone, androstenedione, dehydroepiandrosterone, and dihydrotestosterone) in conditioned culture media. Ovaries were harvested from 12-day-old CD-1 mice and cultured for 28 days, with ovulation induction on culture day 14. Media were supplemented human chorionic gonadotropin (hCG, a luteinizing hormone analog) and follicle stimulating hormone (FSH) at ratios of 1:0 (standard media), 1:1 (physiologic ratio), and 3:1 (PCOS-like ratio). Ovaries cultured in PCOS-like media displayed hyperandrogenism and impaired ovulation, two key features of a PCOS-like phenotype. Taken together, this first-of-its-kind presentation of hormone levels from single tissues creates a map of the enzymatic steps most acutely affected by gonadotropin dysregulation and may provide opportunities for assessing other potential insults in PCOS pathogenesis.

Impact of dissolved oxygen and pH on the removal of selenium from water by iron electrocoagulation.

Removing dissolved selenium (i.e., selenate and selenite) from wastewater is a challenging issue for a range of industries. Iron electrocoagulation can produce Fe(II)-containing solids that can adsorb and chemically reduce dissolved Se. In a series of bench-scale experiments we investigated the effects of dissolved oxygen (fully oxic, partially oxic, and strictly anoxic) and pH (6 and 8) on the rate and extent of dissolved selenate and selenite removal by iron electrocoagulation. These studies combined measurements of the aqueous phase with the direct characterization of the resulting solids. Among the conditions studied the rate and extent of dissolved selenium (Se) removal were highest at pH 8 and strictly anoxic conditions. X-ray absorption spectroscopy demonstrated that in the absence of oxygen, Se was primarily transformed to elemental selenium (Se0) and selenide. Green rust that formed in the suspension during electrocoagulation played a key role as a reductant and sorbent of Se. At pH 6 dissolved oxygen did not affect the rates and extents of dissolved Se removal. Under all the conditions studied, dissolved Se removal was more effective with iron electrocoagulation than with the direct addition of pre-synthesized green rust or ferrous hydroxide. The most rapid and substantial dissolved Se removal was achieved by freshly-formed green rust and ferrous hydroxide, which are both Fe(II)-bearing solids. With an improved understanding of the products and mechanisms of the process, iron electrocoagulation can be optimized for removal of Se from wastewater.

Human Serum Albumin Cys34 Adducts in Newborn Dried Blood Spots: Associations With Air Pollution Exposure During Pregnancy.

Background: Increasing evidence suggests that exposure to air pollution during pregnancy is associated with adverse pregnancy outcomes. However, biomarkers associated with air pollution exposure are widely lacking and often transient. In addition, ascertaining biospecimens during pregnacy to assess the prenatal environment remains largely infeasible. Objectives: To address these challenges, we investigated relationships between air pollution exposure during pregnancy and human serum albumin Cys34 (HSA-Cys34) adducts in newborn dried blood spots (DBS) samples, which captures an integration of perinatal exposures to small reactive molecules in circulating blood. Methods: Newborn DBS were obtained from a state archive for a cohort of 120 children born at one Kaiser Permanente Southern California (KPSC) hospitals in 2007. These children were selected to maximize the range of residential air pollution exposure during the entire pregnancy to PM2.5, PM10, NO2, O3, based on monthly estimates interpolated from regulatory monitoring sites. HSA-Cys34 adducts were selected based on previously reported relationships with air pollution exposure and oxidative stress. Results: Six adducts measured in newborn DBS samples were associated with air pollution exposures during pregnancy; these included direct oxidation products, adducts formed with small thiol compounds, and adducts formed with reactive aldehydes. Two general trends were identified: Exposure to air pollution late in pregnancy (i.e., in the last 30 days) was associated with increased oxidative stress, and exposure to air pollution earlier in pregnancy (i.e., not in the last 30 days) was associated with decreased oxidative stress around the time of birth. Discussion: Air pollution exposure occurring during pregnancy can alter biology and leave measurable impacts on the developing infant captured in the newborn DBS adductome, which represents a promising tool for investigating adverse birth outcomes in population-based studies.

Impact of orthophosphate on lead release from pipe scale in high pH, low alkalinity water.

This study explored the ability of orthophosphate addition to limit lead release from lead service lines delivering high pH, low alkalinity water. We built pipe loop reactors with lead pipes harvested from Providence, RI, and we operated them with high pH and low alkalinity water of a composition similar to that in Providence. Orthophosphate addition decreased the release of both dissolved and particulate lead to the water. The most substantial decreases in total lead concentrations occurred after 15 weeks of orthophosphate addition, which was associated with the formation of calcium-lead-phosphorus (Ca-Pb-P) solids as part of the pipe scale. Pre-existing hydrocerussite (Pb3(CO3)2(OH)2(s)) in the scale of the lead pipe appeared to promote the formation of a Ca-Pb-P solid similar to phosphohedyphane (Ca2Pb3(PO4)3(Cl,F,OH)(s)). Continuous orthophosphate addition was also associated with the formation of a calcium phosphate solid with features like those of fluorapatite (Ca5(PO4)3F(s)) on the outermost layer of the scale. Through promoting the formation of these new solids within and on top of the scales, orthophosphate addition limited release of dissolved and particulate lead. These results demonstrate the ability of orthophosphate to control lead release at higher pH conditions than those for which it has typically been used. In addition to the formation of phosphate solids, PbO2(s), which was not present on the as-received pipes, was formed due to the constant supply of free chlorine in the laboratory-scale experiment.

Effect of Aluminum on Lead Release to Drinking Water from Scales of Corrosion Products.

The occurrence of aluminum in scales on lead pipes is common. This study aimed to identify factors that influence Al accumulation on oxidized lead surfaces and to determine whether the presence of Al impacts Pb release from corrosion products to water. Al accumulation and Pb release were monitored both with and without the addition of phosphate as a corrosion inhibitor. Pb coupons with corrosion scales were exposed to chlorinated water for up to 198 days to investigate Al accumulation and Pb release. Al accumulation was facilitated by Pb corrosion products, but its accumulation was inhibited by phosphate addition. During the study period, the formation of Al deposits did not affect Pb release when phosphate was absent. In an Al-free system, the addition of 1.0 mg/L phosphate (as P) lowered the dissolved Pb concentration below 1.0 µg/L. In a system containing 200 µg/L Al, the emergence of phosphate's effect on Pb control was delayed, and the dissolved Pb concentration decreased but stabilized at a higher value (10-12 µg/L) than in the Al-free system. Phosphohedyphane (Ca2Pb3(PO4)3Cl) was formed in all phosphate-containing systems, and PbO2 was formed independent of phosphate addition. The effect of Al on Pb release was probably related to its influence on the composition and morphology of Pb-containing minerals on coupon surfaces. The laboratory study has unavoidable limitations in its ability to simulate all conditions in real lead service lines, but this study still highlights the importance of considering the influence of Al when designing Pb corrosion control strategies.

The Ability of Phosphate To Prevent Lead Release from Pipe Scale When Switching from Free Chlorine to Monochloramine.

For lead pipes that contain PbO2(s) as a major component of their scales, a change in the residual disinfectant from free chlorine to monochloramine can destabilize the PbO2(s) and result in dramatic increases in aqueous lead concentrations. Such a scenario occurred in Washington, D.C., in late 2000. That problem was ultimately addressed by the addition of phosphate as a corrosion inhibitor, but it took several months for lead levels to drop below regulatory values. This study sought to determine whether adding phosphate prior to switching the disinfectant could mitigate lead release. Using synthetic tap water and new lead pipes, we developed a set of lead pipes with scales rich in PbO2(s) and then studied their response to a change from free chlorine to monochloramine. Total lead concentrations remained below 10 µg/L for pipes that received phosphate prior to and during the switch. In contrast, total lead concentrations increased from less than 5 µg/L to more than 150 µg/L as a result of the disinfectant switch when phosphate was not present. Characterization of the pipe scales demonstrated that plattnerite (ß-PbO2(s)) was the dominant component of the scale prior to the switch, and that the scale gradually transformed into one containing a lead phosphate solid chemically similar to phosphohedyphane (Ca2Pb3(PO4)3(Cl,F,OH)(s)) when phosphate was present.

Role of Manganese in Accelerating the Oxidation of Pb(II) Carbonate Solids to Pb(IV) Oxide at Drinking Water Conditions.

Pb(II) carbonate solids are corrosion products that form on the inner surfaces of lead service lines (LSLs) and can be oxidized by free chlorine to form Pb(IV) oxide (PbO2). The formation of PbO2 can maintain low dissolved lead concentrations in drinking water, but PbO2 can dissolve if a free chlorine residual is not maintained. Experiments demonstrated that the oxidation of Pb(II) carbonate by free chlorine was faster with manganese (Mn). Without Mn(II), the oxidation of Pb(II) carbonate was an autocatalytic process. With Mn(II), the overall oxidation rate was 2 orders of magnitude faster than without Mn(II). X-ray diffraction and free chlorine consumption profiles indicated that δ-MnO2 was formed within several minutes of the reaction of Mn(II) with free chlorine, and δ-MnO2 catalyzed the oxidation of Pb(II) carbonate by free chlorine. Free chlorine consumption profiles for Pb(II) carbonate with and without Mn(II) were interpreted based on the kinetics and stoichiometry of the underlying chemical reactions. These findings highlight the importance of Mn in accelerating the formation of PbO2 in water with Pb(II) carbonate solids and free chlorine, and it may help explain why PbO2 is observed on LSLs of some but not all water systems that use free chlorine.

Formation and Aggregation of Lead Phosphate Particles: Implications for Lead Immobilization in Water Supply Systems.

Phosphate is commonly added to drinking water to inhibit lead release from lead service lines and lead-containing materials in premise plumbing. Phosphate addition promotes the formation of lead phosphate particles, and their aggregation behaviors may affect their transport in pipes. Here, lead phosphate formation and aggregation were studied under varied aqueous conditions typical of water supply systems. Under high aqueous PO4/Pb molar ratios (>1), phosphate adsorption made the particles more negatively charged. Therefore, enhanced stability of lead phosphate particles was observed, suggesting that although addition of excess phosphate can lower the dissolved lead concentrations in tap water, it may increase concentrations of particulate lead. Adsorption of divalent cations (Ca2+ and Mg2+) onto lead phosphate particles neutralized their negative surface charges and promoted their aggregation at pH 7, indicating that phosphate addition for lead immobilization may be more efficient in harder waters. The presence of natural organic matter (NOM, ≥ 0.05 mg C/L humic acid and ≥ 0.5 mg C/L fulvic acid) retarded particle aggregation at pH 7. Consequently, removal of organic carbon during water treatment to lower the formation of disinfection-byproducts (DBPs) may have the additional benefit of minimizing the mobility of lead-containing particles. This study provided insight into fundamental mechanisms controlling lead phosphate aggregation. Such understanding is helpful to understand the observed trends of total lead in water after phosphate addition in both field and pilot-scale lead pipe studies. Also, it can help optimize lead immobilization by better controlling the water chemistry during phosphate addition.

Transformation impacts of dissolved and solid phase Fe(II) on trichloroethylene (TCE) reduction in an iron-reducing bacteria (IRB) mixed column system: a mathematical model.

In this research, we conducted trichloroethylene (TCE) reduction in a column filled with iron and iron-reducing bacteria (IRB) and developed a mathematical model to investigate the critical reactions between active species in iron/IRB/contaminant systems. The formation of ferrous iron (Fe(II)) in this system with IRB and zero-valent iron (ZVI, Fe(0)) coated with a ferric iron (Fe(III)) crust significantly affected TCE reduction and IRB respiration in various ways. This study presents a new framework for transformation property and reducing ability of both dissolved (Fe(II)(dissolved)) and solid form ferrous iron (Fe(II)(solid)). Results showed that TCE reduction was strongly depressed by Fe(II)(solid) rather than by other inhibitors (e.g., Fe(III) and lactate), suggesting that Fe(II)(solid) might reduce IRB activation due to attachment to IRB cells. Newly exposed Fe(0) from the released Fe(II)(dissolved) was a strong contributor to TCE reduction compared to Fe(II)(solid). In addition, our research confirmed that less Fe(II)(solid) production strongly supported long-term TCE reduction because it may create an easier TCE approach to Fe(0) or increase IRB growth. Our findings will aid the understanding of the contributions of iron media (e.g., Fe(II)(solid), Fe(II)(dissolved), Fe(III), and Fe(0)) to IRB for decontamination in natural groundwater systems.