Effects of HCl pretreatment, drying, and storage on the stable isotope ratios of soil and sediment samples.

RATIONALE: Stable isotope (δ(13) C, δ(15) N, δ(34) S values) analysis has become increasingly important for tracing contaminant sources in environments. Pretreatment of environmental samples allows accurate analysis of stable isotope ratios. The pretreatment of a sample and its subsequent preservation could either contaminate or create experimental artifacts affecting the validity of the resulting C/N ratios and the elemental isotopic contents of a sample. METHODS: The effects of acid pretreatment (0.1, 0.5, 1, 2, 5, 13 M HCl) and exposure period (2, 6, 12, 24, and 48 h) on the stable isotopic ratios of marine sediment (MS), river sediment (RS) and terrestrial soil (TS) samples were evaluated. The effects of storage temperatures (-80, -20 and 2°C), storage duration (1 week, 1 to 12 months) and washing steps (1, 2, 3, 5, 7 or 12 times) on the stable isotopic ratios were also considered. The %C, %N and %S, as well as the δ(13) C, δ(15) N, and δ(34) S values, of each sample were measured using continuous flow Elemental Analyzer/Isotope Ratio Mass Spectrometry (EA/IRMS). RESULTS: The HCl treatment was applicable for δ(13) C analysis. However, the acid concentration and duration of exposure that brought about total removal of carbonate for the three sample types varied; e.g. the TS sample required stronger acid and a shorter exposure time. Storage time also had an effect: the δ(13) C values were lower and the δ(15) N and δ(34) S values higher after storage for 300 days. CONCLUSIONS: HCl pretreatment effectively eliminates carbonates and thereby helps δ(13) C analysis of the organic fraction. HCl pretreatment is not recommended for δ(15) N and δ(34) S analysis. Freeze-drying of samples is recommended rather than oven drying. A temperature-dependent change in the isotopic ratios of long-term stored samples was observed during this study; therefore, relatively short-term storage (-80°C) of freeze-dried samples is preferable. Copyright © 2016 John Wiley & Sons, Ltd.

Geographic clustering of elevated blood heavy metal levels in pregnant women.

BACKGROUND: Cadmium (Cd), lead (Pb), mercury (Hg), and arsenic (As) exposure is ubiquitous and has been associated with higher risk of growth restriction and cardiometabolic and neurodevelopmental disorders. However, cost-efficient strategies to identify at-risk populations and potential sources of exposure to inform mitigation efforts are limited. The objective of this study was to describe the spatial distribution and identify factors associated with Cd, Pb, Hg, and As concentrations in peripheral blood of pregnant women. METHODS: Heavy metals were measured in whole peripheral blood of 310 pregnant women obtained at gestational age ~12 weeks. Prenatal residential addresses were geocoded and geospatial analysis (Getis-Ord Gi* statistics) was used to determine if elevated blood concentrations were geographically clustered. Logistic regression models were used to identify factors associated with elevated blood metal levels and cluster membership. RESULTS: Geospatial clusters for Cd and Pb were identified with high confidence (p-value for Gi* statistic <0.01). The Cd and Pb clusters comprised 10.5 and 9.2 % of Durham County residents, respectively. Medians and interquartile ranges of blood concentrations (µg/dL) for all participants were Cd 0.02 (0.01-0.04), Hg 0.03 (0.01-0.07), Pb 0.34 (0.16-0.83), and As 0.04 (0.04-0.05). In the Cd cluster, medians and interquartile ranges of blood concentrations (µg/dL) were Cd 0.06 (0.02-0.16), Hg 0.02 (0.00-0.05), Pb 0.54 (0.23-1.23), and As 0.05 (0.04-0.05). In the Pb cluster, medians and interquartile ranges of blood concentrations (µg/dL) were Cd 0.03 (0.02-0.15), Hg 0.01 (0.01-0.05), Pb 0.39 (0.24-0.74), and As 0.04 (0.04-0.05). Co-exposure with Pb and Cd was also clustered, the p-values for the Gi* statistic for Pb and Cd was <0.01. Cluster membership was associated with lower education levels and higher pre-pregnancy BMI. CONCLUSIONS: Our data support that elevated blood concentrations of Cd and Pb are spatially clustered in this urban environment compared to the surrounding areas. Spatial analysis of metals concentrations in peripheral blood or urine obtained routinely during prenatal care can be useful in surveillance of heavy metal exposure.

Passive ammonia monitoring in the United States: comparing three different sampling devices.

The need for ambient gaseous ammonia (NH(3)) measurements has increased in the last decade as reactive NH(3) concentrations and deposition fluxes show little change even with tightening standards on nitrogen oxides (NO(x)) emissions. Currently, there are several networks developing methods for adding NH(3) measurements in the U.S. Gaseous NH(3) measurements will provide scientists and policymakers data which can be used to estimate ecosystem inputs, validate air quality models including trends and regional variability, and evaluate changes to the environment based on additional emission reduction requirements and estimates of critical nitrogen load exceedances. The passive samplers described in this paper were deployed in duplicate or triplicate and collocated with annular denuders or continuous instruments to determine their accuracy. The samplers assessed included the Adapted Low-Cost Passive High Absorption (ALPHA), Radiello(®), and Ogawa passive samplers. The median relative percent differences (MRPD) between the reference method and passive samplers for the ALPHA, Radiello(®) and Ogawa were -2.4%, -37% and -44%, respectively. The precision between duplicate samplers for the ALPHA and Ogawa samplers, was 7% and 6%, respectively. Triplicate Radiello(®) precision was assessed using the coefficient of variation (CV). The CV for the Radiello(®) samplers was 10%. This article discusses the statistical results from these studies.

Modeling and measurements of ammonia from poultry operations: Their emissions, transport, and deposition in the Chesapeake Bay.

The goal of this study is to determine how much ammonia/nitrogen is being deposited to the Maryland Eastern Shore land and the Chesapeake Bay from poultry operations on Maryland's Eastern Shore. We simulated the fate of ammonia/nitrogen emitted (using emission factors from the U.S. EPA in conjunction with Carnegie-Mellon University) from 603 poultry facilities using the air quality model, AERMOD. The model domain was approximately 134 km by 230 km (and covers the full land area of Maryland's Eastern Shore), with a horizontal resolution of 2 km by 2 km. Ammonia concentration observations were made at 23 sites across Maryland's Eastern Shore during two periods (September and October 2017) in order to calibrate the model. An ammonia deposition velocity of 2.4 cm/sec was selected based on the sensitivity analysis of results for the simulation of a large poultry facility, and this value fell within the range of measurements reported in the scientific literature downwind of Concentrated Animal Feeding Operations (CAFOs). The ammonia deposition velocity of 2.4 cm/s leads to an estimated total annual ammonia deposition of 11,100 Megagrams/year (10,600 Mg/yr deposition to land, and 508 Mg/yr deposition to water (1 Mg = 1,000,000 g = 1.1023 US Tons)). In addition, model simulations indicate that ~72.4% of ammonia emissions from poultry animal feeding operations would be deposited within the modeling domain. However, this deposited ammonia/nitrogen may be transported through waterways from the land mass and ground water to the Chesapeake Bay. A comprehensive sensitivity analysis of the assumed ammonia deposition velocity (ranging from 0.15 to 3.0 cm/s) on estimated ammonia annual deposition is provided. Using the lower limit of an ammonia deposition velocity of 0.15 cm/s gives much smaller estimated total annual ammonia deposition of 2,040 Mg/yr (1,880 Mg/yr deposition to land and 163 Mg/yr deposition to water).

Characterization of eversion syndrome in captive Scyphomedusa jellyfish.

OBJECTIVE: To determine whether Scyphomedusa jellyfish with eversion syndrome had alterations in husbandry conditions, elemental content, or histologic appearance, compared with unaffected jellyfish. ANIMALS: 123 jellyfish (44 with eversion syndrome and 79 without) at 6 institutions. PROCEDURES: Elemental analyses were performed on 24 jellyfish with eversion syndrome and 49 without, and histologic examinations were performed on 20 jellyfish with eversion syndrome and 30 without. A questionnaire distributed to 39 institutions with Scyphomedusa jellyfish was used to gather information about husbandry, environmental conditions, and prevalence of eversion syndrome. RESULTS: For the 39 institutions that responded to the questionnaire, prevalence of eversion syndrome ranged from 0% to 30%. For Aurelia aurita, eversion was more common at institutions with only captive-raised and no wild-caught jellyfish. Eversion was most common among young (approx 1- to 2-month-old) growing jellyfish and older (> 6-month-old) jellyfish. Elemental analysis revealed only minor differences between affected and unaffected jellyfish, with great variation among jellyfish from the same institution and among jellyfish from different institutions. Striated muscle degeneration and necrosis and extracellular matrix (mesoglea) degeneration were evident on histologic examination of affected jellyfish. CONCLUSIONS AND CLINICAL RELEVANCE: Results suggested that eversion syndrome is a complex phenomenon associated with degenerative changes of the bell matrix.

Inorganic PM2.5 at a U.S. agricultural site.

In this study, we present approximately two years (January 1999-December 2000) of atmospheric NH3, NH4+, HCl, Cl-, HNO3, NO3-, SO2, and SO4= concentrations measured by the annular denuder/filter pack method at an agricultural site in eastern North Carolina. This site is influenced by high NH3 emissions from animal production and fertilizer use in the surrounding area and neighboring counties. The two-year mean NH3 concentration is 5.6 (+/-5.13) microg m(-3). The mean concentration of total inorganic PM2.5, which includes SO4=, NO3-, NH4+, and Cl-, is 8.0 (+/-5.84) microg m(-3). SO4=, NO3-, NH4+, and Cl- represent, respectively, 53, 24, 22, and 1% of measured inorganic PM2.5. NH3 contributes 72% of total NH3 + NH4+, on an average. Equilibrium modeling of the gas+aerosol NH3/H2SO4/HNO3 system shows that inorganic PM2.5 is more sensitive to reductions in gas + aerosol concentrations of sulfate and nitrate relative to NH3.

Volatile organic compounds at swine facilities: a critical review.

Volatile organic compounds (VOCs) are regulated aerial pollutants that have environmental and health concerns. Swine operations produce and emit a complex mixture of VOCs with a wide range of molecular weights and a variety of physicochemical properties. Significant progress has been made in this area since the first experiment on VOCs at a swine facility in the early 1960s. A total of 47 research institutions in 15 North American, European, and Asian countries contributed to an increasing number of scientific publications. Nearly half of the research papers were published by U.S. institutions. Investigated major VOC sources included air inside swine barns, in headspaces of manure storages and composts, in open atmosphere above swine wastewater, and surrounding swine farms. They also included liquid swine manure and wastewater, and dusts inside and outside swine barns. Most of the sample analyses have been focusing on identification of VOC compounds and their relationship with odors. More than 500 VOCs have been identified. About 60% and 10% of the studies contributed to the quantification of VOC concentrations and emissions, respectively. The largest numbers of VOC compounds with reported concentrations in a single experimental study were 82 in air, 36 in manure, and 34 in dust samples. The relatively abundant VOC compounds that were quantified in at least two independent studies included acetic acid, butanoic acid (butyric acid), dimethyl disulfide, dimethyl sulfide, iso-valeric, p-cresol, propionic acid, skatole, trimethyl amine, and valeric acid in air. They included acetic acid, p-cresol, iso-butyric acid, butyric acid, indole, phenol, propionic acid, iso-valeric acid, and skatole in manure. In dust samples, they were acetic acid, propionic acid, butyric acid, valeric acid, p-cresol, hexanal, and decanal. Swine facility VOCs were preferentially bound to smaller-size dusts. Identification and quantification of VOCs were restricted by using instruments based on gas Chromatography (GC) and liquid chromatography (LC) with different detectors most of which require time-consuming procedures to obtain results. Various methodologies and technologies in sampling, sample preparation, and sample analysis have been used. Only four publications reported using GC based analyzers and PTR-MS (proton-transfer-reaction mass spectrometry) that allowed continuous VOC measurement. Because of this, the majority of experimental studies were only performed on limited numbers of air, manure, or dust samples. Many aerial VOCs had concentrations that were too low to be identified by the GC peaks. Although VOCs emitted from swine facilities have environmental concerns, only a few studies investigated VOC emission rates, which ranged from 3.0 to 176.5mgd(-1)kg(-1) pig at swine finishing barns and from 2.3 to 45.2gd(-1)m(-2) at manure storages. Similar to the other pollutants, spatial and temporal variations of aerial VOC concentrations and emissions existed and were significantly affected by manure management systems, barn structural designs, and ventilation rates. Scientific research in this area has been mainly driven by odor nuisance, instead of environment or health concerns. Compared with other aerial pollutants in animal agriculture, the current scientific knowledge about VOCs at swine facilities is still very limited and far from sufficient to develop reliable emission factors.

Estimation of in-canopy ammonia sources and sinks in a fertilized Zea mays field.

An analytical model was developed to describe in-canopy vertical distribution of ammonia (NH(3)) sources and sinks and vertical fluxes in a fertilized agricultural setting using measured in-canopy mean NH(3) concentration and wind speed profiles. This model was applied to quantify in-canopy air-surface exchange rates and above-canopy NH(3) fluxes in a fertilized corn (Zea mays) field. Modeled air-canopy NH(3) fluxes agreed well with independent above-canopy flux estimates. Based on the model results, the urea fertilized soil surface was a consistent source of NH(3) one month following the fertilizer application, whereas the vegetation canopy was typically a net NH(3) sink with the lower portion of the canopy being a constant sink. The model results suggested that the canopy was a sink for some 70% of the estimated soil NH(3) emissions. A logical conclusion is that parametrization of within-canopy processes in air quality models are necessary to explore the impact of agricultural field level management practices on regional air quality. Moreover, there are agronomic and environmental benefits to timing liquid fertilizer applications as close to canopy closure as possible. Finally, given the large within-canopy mean NH(3) concentration gradients in such agricultural settings, a discussion about the suitability of the proposed model is also presented.

Cellular uptake of gold nanoparticles passivated with BSA-SV40 large T antigen conjugates.

Internalization and subcellular localization in HeLa cells of gold nanoparticles modified with the SV40 large T antigen were quantified using inductively coupled plasma optical emission spectroscopy (ICP-OES). Internalization was monitored as a function of incubation time, temperature, nanoparticle diameter, and large T surface coverage. Increasing the amount of large T peptides per gold nanoparticle complex, by either increasing the coverage at constant nanoparticle diameter or by increasing the nanoparticle diameter at constant large T coverage, resulted in more cellular internalization. In addition, nuclear fractionation was performed to quantify nuclear localization of these complexes as a function of large T coverage. In contrast to our prior qualitative investigations of nuclear localization by video-enhanced color differential interference contrast microscopy (VEC-DIC), ICP-OES was able to detect nanoparticles inside fractionated cell nuclei. Although increasing the large T coverage was found to afford higher cell internalization and nuclear targeting, quantitative evaluation of cytotoxicity revealed that higher large T coverages also resulted in greater cytotoxicity. The ICP-OES and nuclear fractionation techniques reported here are valuable tools that can add important quantitative information to optical and electron imaging methods such as VEC-DIC and transmission electron microscopy regarding the fate of nanoparticles in cells.