TXRF analysis of soils and sediments to assess environmental contamination

Total reflection x-ray fluorescence spectroscopy (TXRF) is proposed for the elemental chemical analysis of crustal environmental samples, such as sediments and soils. A comparative study of TXRF with respect to flame atomic absorption spectroscopy and inductively coupled plasma optical emission spectroscopy was performed. Microwave acid digestion and suspension preparation methods are evaluated. A good agreement was found among the results obtained with different spectroscopic techniques and sample preparation methods for Cr, Mn, Fe, Ni, Cu, and Zn. We demonstrated that TXRF is suitable for the assessment of environmental contamination phenomena, even if the errors for Pb, As, V, and Ba are ingent.     

Source apportion of atmospheric particulate matter: a joint Eulerian/Lagrangian approach

PM_2.5 samples were collected during an annual monitoring campaign (January 2012–January 2013) in the urban area of Naples, one of the major cities in Southern Italy. Samples were collected by means of a standard gravimetric sampler (Tecora Echo model) and characterized from a chemical point of view by ion chromatography. As a result, 143 samples together with their ionic composition have been collected. We extend traditional source apportionment techniques, usually based on multivariate factor analysis, interpreting the chemical analysis results within a Lagrangian framework. The Hybrid Single-Particle Lagrangian Integrated Trajectory Model (HYSPLIT) model was used, providing linkages to the source regions in the upwind areas. Results were analyzed in order to quantify the relative weight of different source types/areas. Model results suggested that PM concentrations are strongly affected not only by local emissions but also by transboundary emissions, especially from the Eastern and Northern European countries and African Saharan dust episodes.     

Investigations on mobility of carbon colloid supported nanoscale zero-valent iron (nZVI) in a column experiment and a laboratory 2D-aquifer test system

Nanoscale zero-valent iron (nZVI) has recently gained great interest in the scientific community as in situ reagent for installation of permeable reactive barriers in aquifer systems, since nZVI is highly reactive with chlorinated compounds and may render them to harmless substances. However, nZVI has a high tendency to agglomerate and sediment; therefore it shows very limited transport ranges. One new approach to overcome the limited transport of nZVI in porous media is using a suited carrier colloid. In this study we tested mobility of a carbon colloid supported nZVI particle “Carbo-Iron Colloids” (CIC) with a mean size of 0.63 μm in a column experiment of 40 cm length and an experiment in a two-dimensional (2D) aquifer test system with dimensions of 110?×?40?×?5 cm. Results show a breakthrough maximum of 82 % of the input concentration in the column experiment and 58 % in the 2D-aquifer test system. Detected residuals in porous media suggest a strong particle deposition in the first centimeters and few depositions in the porous media in the further travel path. Overall, this suggests a high mobility in porous media which might be a significant enhancement compared to bare or polyanionic stabilized nZVI.     

Mercury accumulation and tissue-specific antioxidant efficiency in the wild European sea bass (Dicentrarchus labrax) with emphasis on seasonality

The main goal of this study was to assess both mercury (Hg) accumulation and organs’ specific oxidative stress responses of gills, liver and kidney of Dicentrarchus labrax with emphasis on seasonality. Fish were collected in cold and warm periods in three stations: reference, moderated and highly contaminated sites. Our results showed that seasonal factors slightly influenced Hg accumulation between year periods (cold and warm) and strongly affected organs’ response basal levels. In contrast, seasonality seemed not to influence oxidative stress responses, since similar response patterns were obtained for both year periods, and moderate degree of antioxidant responses was obtained. Moreover, the oxidative stress profile may be attributed to Hg contamination degree, which showed organ-specific response and accumulation patterns. Hence, gills showed to be able to adapt to Hg contamination, and in opposition, kidney and liver demonstrated some vulnerability to Hg toxicity. The critical Hg concentrations indicated specific threshold limits for each organ. Overall, seasonality should be taken into account in monitoring programmes, helping to characterize the individuals’ reference values of response and thus to discriminate between the effects induced by natural causes or by contamination.     

Outdoor fine and ultrafine particle measurements at six bus stops with smoking on two California arterial highways—Results of a pilot study

As indoor smoking bans have become widely adopted, some U.S. communities are considering restricting smoking outdoors, creating a need for measurements of air pollution near smokers outdoors. Personal exposure experiments were conducted with four to five participants at six sidewalk bus stops located 1.5–3.3 m from the curb of two heavily traveled California arterial highways with 3300–5100 vehicles per hour. At each bus stop, a smoker in the group smoked a cigarette. Gravimetrically calibrated continuous monitors were used to measure fine particle concentrations (aerodynamic diameter ≤2.5 µm; PM_2.5) in the breathing zones (within 0.2 m from the nose and mouth) of each participant. At each bus stop, ultrafine particles (UFP), wind speed, temperature, relative humidity, and traffic counts were also measured. For 13 cigarette experiments, the mean PM_2.5 personal exposure of the nonsmoker seated 0.5 m from the smoker during a 5-min cigarette ranged from 15 to 153 µg/m³. Of four persons seated on the bench, the smoker received the highest PM_2.5 breathing-zone exposure of 192 µg/m³. There was a strong proximity effect: nonsmokers at distances 0.5, 1.0, and 1.5 m from the smoker received mean PM_2.5 personal exposures of 59, 40, and 28 µg/m³, respectively, compared with a background level of 1.7 µg/m³. Like the PM_2.5 concentrations, UFP concentrations measured 0.5 m from the smoker increased abruptly when a cigarette started and decreased when the cigarette ended, averaging 44,500 particles/cm³ compared with the background level of 7200 particles/cm³. During nonsmoking periods, the UFP background concentrations showed occasional peaks due to traffic, whereas PM_2.5 background concentrations were extremely low. The results indicate that a single cigarette smoked outdoors at a bus stop can cause PM_2.5 and UFP concentrations near the smoker that are 16–35 and 6.2 times, respectively, higher than the background concentrations due to cars and trucks on an adjacent arterial highway.

Implications: Rules banning smoking indoors have been widely adopted in the United States and in many countries. Some communities are considering smoking bans that would apply to outdoor locations. Although many measurements are available of pollutant concentrations from secondhand smoke at indoor locations, few measurements are available of exposure to secondhand smoke outdoors. This study provides new data on exposure to fine and ultrafine particles from secondhand smoke near a smoker outdoors. The levels are compared with the exposure measured next to a highway. The findings are important for policies that might be developed for reducing exposure to secondhand smoke outdoors.     

Characterization of indoor air quality and resident health in an Arizona senior housing apartment building

A survey of key indoor air quality (IAQ) parameters and resident health was carried out in 72 apartments within a single low-income senior housing building in Phoenix, Arizona. Air sampling was carried out simultaneously with a questionnaire on personal habits and general health of residents. Mean PM₁₀ concentrations are 66±16, 58±13, and 24±3 μg/m³ and mean PM_2.5 concentrations are 62±16, 53±13, and 20±2 μg/m³ for the living room, kitchen, and outdoor balcony, respectively. Median PM₁₀ concentrations are 17, 18 and 17 μg/m³ and median PM_2.5 concentrations are 13, 14, and 13 μg/m³, respectively. The initial results indicate that increased indoor particle concentrations coincide with residents who report smoking cigarettes. Indoor formaldehyde concentrations revealed median levels of 36.9, 38.8, and 4.3 ppb in the living room, kitchen, and balcony, respectively. Results show that 36% of living room samples and 44% of kitchen samples exceeded the Health Canada REL for chronic exposure to formaldehyde (40 ppb). Associations between occupants’ behavior, self-reported health conditions, and IAQ are evaluated.

Implications:This study provides a characterization of indoor air quality (IAQ) of subsidized apartments for seniors in Phoenix, Arizona. It is important for policy makers to understand the environments in which low-income seniors live, as they are vulnerable to the health impacts from poor IAQ. Formaldehyde concentrations were found to exceed the Health Canada 8-hr reference exposure level (REL) for up to 44% of indoor samples. Particulate matter exposure was governed by resident behavior (i.e., smoking). Associations between occupants’ behavior, IAQ, and self-reported health conditions are evaluated. This work can provide a foundation for subsequent remediation of IAQ conditions.     

Urban impacts on regional carbonaceous aerosols: Case study in central Texas

Rural and background sites provide valuable information on the concentration and optical properties of organic, elemental, and water-soluble organic carbon (OC, EC, and WSOC), which are relevant for understanding the climate forcing potential of regional atmospheric aerosols. To quantify climate- and air quality-relevant characteristics of carbonaceous aerosol in the central United States, a regional background site in central Texas was chosen for long-term measurement. Back trajectory (BT) analysis, ambient OC, EC, and WSOC concentrations and absorption parameters are reported for the first 15 months of a long-term campaign (May 2011–August 2012). BT analysis indicates consistent north–south airflow connecting central Texas to the Central Plains. Central Texas aerosols exhibited seasonal trends with increased fine particulate matter (<2.5 μm aerodynamic diameter, PM_2.5) and OC during the summer (PM_2.5 = 10.9 μg m^?3 and OC = 3.0 μg m^?3) and elevated EC during the winter (0.22 μg m^?3). When compared to measurements in Dallas and Houston, TX, central Texas OC appears to have mixed urban and rural sources. However, central Texas EC appears to be dominated by transport of urban emissions. WSOC averaged 63% of the annual OC, with little seasonal variability in this ratio. To monitor brown carbon (BrC), absorption was measured for the aqueous WSOC extracts. Light absorption coefficients for EC and BrC were highest during summer (EC MAC = 11 m² g^?1 and BRC MAE₃₆₅ = 0.15 m² g^?1). Results from optical analysis indicate that regional aerosol absorption is mostly due to EC with summertime peaks in BrC attenuation. This study represents the first reported values of WSOC absorption, MAE₃₆₅, for the central United States.

Implications:Background concentration and absorption measurements are essential in determining regional potential radiative forcing due to atmospheric aerosols. Back trajectory, chemical, and optical analysis of PM_2.5 was used to determine climatic and air quality implications of urban outflow to a regional receptor site, representative of the central United States. Results indicate that central Texas organic carbon has mixed urban and rural sources, while elemental carbon is controlled by the transport of urban emissions. Analysis of aerosol absorption showed black carbon as the dominant absorber, with less brown carbon absorption than regional studies in California and the southeastern United States.     

Comparative statistical study of hourly precipitation determined by radar-based Stage IV and ground-based methods in the North Central United States

Detailed hourly precipitation data are required for long-range modeling of dispersion and wet deposition of particulate matter and water-soluble pollutants using the CALPUFF model. In sparsely populated areas such as the north central United States, ground-based precipitation measurement stations may be too widely spaced to offer a complete and accurate spatial representation of hourly precipitation within a modeling domain. The availability of remotely sensed precipitation data by satellite and the National Weather Service array of next-generation radars (NEXRAD) deployed nationally provide an opportunity to improve on the paucity of data for these areas. Before adopting a new method of precipitation estimation in a modeling protocol, it should be compared with the ground-based precipitation measurements, which are currently relied upon for modeling purposes. This paper presents a statistical comparison between hourly precipitation measurements for the years 2006 through 2008 at 25 ground-based stations in the north central United States and radar-based precipitation measurements available from the National Center for Environmental Predictions (NCEP) as Stage IV data at the nearest grid cell to each selected precipitation station. It was found that the statistical agreement between the two methods depends strongly on whether the ground-based hourly precipitation is measured to within 0.1 in/hr or to within 0.01 in/hr. The results of the statistical comparison indicate that it would be more accurate to use gridded Stage IV precipitation data in a gridded dispersion model for a long-range simulation, than to rely on precipitation data interpolated between widely scattered rain gauges.

Implications:

The current reliance on ground-based rain gauges for precipitation events and hourly data for modeling of dispersion and wet deposition of particulate matter and water-soluble pollutants results in potentially large discontinuity in data coverage and the need to extrapolate data between monitoring stations. The use of radar-based precipitation data, which is available for the entire continental United States and nearby areas, would resolve these data gaps and provide a complete and accurate spatial representation of hourly precipitation within a large modeling domain.     

Concentrations of mobile source air pollutants in urban microenvironments

Human exposures to criteria and hazardous air pollutants (HAPs) in urban areas vary greatly due to temporal-spatial variations in emissions, changing meteorology, varying proximity to sources, as well as due to building, vehicle, and other environmental characteristics that influence the amounts of ambient pollutants that penetrate or infiltrate into these microenvironments. Consequently, the exposure estimates derived from central-site ambient measurements are uncertain and tend to underestimate actual exposures. The Exposure Classification Project (ECP) was conducted to measure pollutant concentrations for common urban microenvironments (MEs) for use in evaluating the results of regulatory human exposure models. Nearly 500 sets of measurements were made in three Los Angeles County communities during fall 2008, winter 2009, and summer 2009. MEs included in-vehicle, near-road, outdoor, and indoor locations accessible to the general public. Contemporaneous 1- to 15-min average personal breathing zone concentrations of carbon monoxide (CO), carbon dioxide (CO₂), volatile organic compounds (VOCs), nitric oxide (NO), nitrogen oxides (NO_x), particulate matter (<2.5 μm diameter; PM_2.5) mass, ultrafine particle (UFP; <100 nm diameter) number, black carbon (BC), speciated HAPs (e.g., benzene, toluene, ethylbenzene, xylenes [BTEX], 1,3-butadiene), and ozone (O₃) were measured continuously. In-vehicle and inside/outside measurements were made in various passenger vehicle types and in public buildings to estimate penetration or infiltration factors. A large fraction of the observed pollutant concentrations for on-road MEs, especially near diesel trucks, was unrelated to ambient measurements at nearby monitors. Comparisons of ME concentrations estimated using the median ME/ambient ratio versus regression slopes and intercepts indicate that the regression approach may be more accurate for on-road MEs. Ranges in the ME/ambient ratios among ME categories were generally greater than differences among the three communities for the same ME category, suggesting that the ME proximity factors may be more broadly applicable to urban MEs.

Implications:Estimates of population exposure to air pollutants extrapolated from ambient measurements at ambient fixed site monitors or exposure surrogates are prone to uncertainty. This study measured concentrations of mobile source air toxics (MSAT) and related criteria pollutants within in-vehicle, outdoor near-road, and indoor urban MEs to provide multipollutant ME measurements that can be used to calibrate regulatory exposure models.     

U.S. National PM2.5 Chemical Speciation Monitoring Networks—CSN and IMPROVE: Description of networks

The U.S. Environmental Protection Agency (EPA) initiated the national PM_2.5 Chemical Speciation Monitoring Network (CSN) in 2000 to support evaluation of long-term trends and to better quantify the impact of sources on particulate matter (PM) concentrations in the size range below 2.5 μm aerodynamic diameter (PM_2.5; fine particles). The network peaked at more than 260 sites in 2005. In response to the 1999 Regional Haze Rule and the need to better understand the regional transport of PM, EPA also augmented the long-existing Interagency Monitoring of Protected Visual Environments (IMPROVE) visibility monitoring network in 2000, adding nearly 100 additional IMPROVE sites in rural Class 1 Areas across the country. Both networks measure the major chemical components of PM_2.5 using historically accepted filter-based methods. Components measured by both networks include major anions, carbonaceous material, and a series of trace elements. CSN also measures ammonium and other cations directly, whereas IMPROVE estimates ammonium assuming complete neutralization of the measured sulfate and nitrate. IMPROVE also measures chloride and nitrite. In general, the field and laboratory approaches used in the two networks are similar; however, there are numerous, often subtle differences in sampling and chemical analysis methods, shipping, and quality control practices. These could potentially affect merging the two data sets when used to understand better the impact of sources on PM concentrations and the regional nature and long-range transport of PM_2.5. This paper describes, for the first time in the peer-reviewed literature, these networks as they have existed since 2000, outlines differences in field and laboratory approaches, provides a summary of the analytical parameters that address data uncertainty, and summarizes major network changes since the inception of CSN.

ImplicationsTwo long-term chemical speciation particle monitoring networks have operated simultaneously in the United States since 2001, when the EPA began regular operations of its PM_2.5 Chemical Speciation Monitoring Network (IMPROVE began in 1988). These networks use similar field sampling and analytical methods, but there are numerous, often subtle differences in equipment and methodologies that can affect the results. This paper describes these networks since 2000 (inception of CSN) and their differences, and summarizes the analytical parameters that address data uncertainty, providing researchers and policymakers with background information they may need (e.g., for 2018 PM_2.5 designation and State Implementation Plan process; McCarthy, 2013) to assess results from each network and decide how these data sets can be mutually employed for enhanced analyses. Changes in CSN and IMPROVE that have occurred over the years also are described.