Determination of gaseous polycyclic aromatic hydrocarbons by a simple direct method using thermal desorption–gas chromatography–mass spectrometry

In the last decade, the development of novel analytical methodologies enabled the identification of several environmental pollutants responsible for health problems associated with indoor exposure. Polycyclic aromatic hydrocarbons (PAHs) are among the potential hazardous chemicals present in ambient air. Due to their bioaccumulation potential and carcinogenic/mutagenic effects, 16 PAHs are currently listed as priority air pollutants. The main goal of this work was to implement a new and simple method for sampling and determination of PAHs in air by using a thermal desorption (TD) technique followed by gas chromatography coupled with mass spectrometry analysis. A detailed study was carried out to optimise the experimental method in each of its phases, including (active) sampling, TD and chromatographic analysis. The results demonstrate that this approach allowed the detection and quantification of the six more volatile PAHs, namely, naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, and anthracene. Acceptable precision and good linearity over the explored range were obtained. No carry-over was observed during experimental tests and the method provided a reproducible answer. The applicability of the novel methodology was tested in real environment, namely, on the roof of a building in an urban area, in a domestic kitchen and in a collective car garage. The method enabled the identification of two PAHs in the field samples, specifically, naphthalene (two rings) and phenanthrene (three rings). With regard to PAHs sample composition, the most abundant PAH found, in the three different locations, was naphthalene, accounting for about 84–100 % of the total PAH mass detected.     

Statistical analysis of aerosol species, trace gasses, and meteorology in Chicago

Both canonical correlation analysis (CCA) and principal component analysis (PCA) were applied to atmospheric aerosol and trace gas concentrations and meteorological data collected in Chicago during the summer months of 2002, 2003, and 2004. Concentrations of ammonium, calcium, nitrate, sulfate, and oxalate particulate matter, as well as, meteorological parameters temperature, wind speed, wind direction, and humidity were subjected to CCA and PCA. Ozone and nitrogen oxide mixing ratios were also included in the data set. The purpose of statistical analysis was to determine the extent of existing linear relationship(s), or lack thereof, between meteorological parameters and pollutant concentrations in addition to reducing dimensionality of the original data to determine sources of pollutants. In CCA, the first three canonical variate pairs derived were statistically significant at the 0.05 level. Canonical correlation between the first canonical variate pair was 0.821, while correlations of the second and third canonical variate pairs were 0.562 and 0.461, respectively. The first canonical variate pair indicated that increasing temperatures resulted in high ozone mixing ratios, while the second canonical variate pair showed wind speed and humidity’s influence on local ammonium concentrations. No new information was uncovered in the third variate pair. Canonical loadings were also interpreted for information regarding relationships between data sets. Four principal components (PCs), expressing 77.0 % of original data variance, were derived in PCA. Interpretation of PCs suggested significant production and/or transport of secondary aerosols in the region (PC1). Furthermore, photochemical production of ozone and wind speed’s influence on pollutants were expressed (PC2) along with overall measure of local meteorology (PC3). In summary, CCA and PCA results combined were successful in uncovering linear relationships between meteorology and air pollutants in Chicago and aided in determining possible pollutant sources.     

Sand as a relevant fraction in geochemical studies in intertidal environments

Soil and sediment samples from several intertidal environment exposed to different types of contamination were studied to investigate the importance of grain size in relation to the capacity of the substrates to retain trace metals. The unfractionated samples (referred to as bulk samples) were separated into the following grain/size fractions: fine–coarse sand (2?0.100 mm), very fine sand (0.100?0.050 mm), silt (0.050?0.002 mm), and clay (0.002 mm). The sample into its fractions was carried out was in a glove box under high-purity N₂ atmosphere in order to minimize any alterations to the samples. The bulk samples were characterized in terms of physicochemical properties such as pH, redox potential, and grain size. The total organic carbon (TOC), total sulfur (S), iron (Fe) pyrite, Fe, and manganese (Mn), and trace metals lead (Pb), mercury (Hg), chromium (Cr), and nickel (Ni) were analyzed in the bulk samples and in each fraction. The sand fractions were also examined by scanning electron microscopy (SEM). Comparisons of the above parameters were made between fractions and between each fraction and the corresponding bulk sample. The fine–coarse sand fraction contained high levels of the primary elements of the geochemical processes that occur in marine sedimentary environments such as TOC, total Fe, Mn, and S. The net concentrations of these four elements were higher in the fine-coarse sand fraction than in the very fine sand fraction and were similar to the net concentrations in the silt and clay fractions. Detailed SEM analysis of the sand coarse fraction revealed the presence of Fe and aluminum oxyhydroxide coatings in the oxic layers, whereas the framboidal pyrites and coatings observed in the anoxic layers were Fe sulfides. The presence of the various coatings explains why the trace metal concentrations in the sand fine–coarse fraction were similar to those in the clay fraction and higher than those in the very fine sand fraction. The present results highlight the importance of the sand fraction, which is generally disregarded in geochemical and environmental studies of sedimentary layers.     

Species Distribution Models of Freshwater Stream Fishes in Maryland and Their Implications for Management

Species distribution models (SDMs) are often used in conservation planning, but their utility can be improved by assessing the relationships between environmental and species response variables. We constructed SDMs for 30 stream fishes of Maryland, USA, using watershed attributes as environmental variables and presence/absence as species responses. SDMs showed substantial agreement between observed and predicted values for 17 species. Most important variables were natural attributes (e.g., ecoregion, watershed area, latitude/longitude); land cover (e.g., %impervious, %row crop) was important for three species. Focused analyses on four representative species (central stoneroller, creek chub, largemouth bass, and white sucker) showed the probability of presence of each species increased non-linearly with watershed area. For these species, SDMs built to predict absent, low, and high densities were similar to presence/absence predictions but provided probable locations of high densities (e.g., probability of high-density creek chub decreased rapidly with watershed area). We applied SDMs to predict suitability of watersheds within the study area for each species. Maps of suitability and the environmental and species response relationships can help develop better management plans.     

An Approach to Reaeration Coefficient Modeling in Local Surface Water Quality Monitoring

Reaeration coefficient (k ₂) for River Atuwara, Ogun State, Nigeria was calculated from dissolved oxygen and biochemical oxygen demand data collected over period of 3 months covering the two prevailing climatic seasons in the country. Both the Akaike and Bayesian information criteria were used in the selection and analysis of ten models to identify the most suitable reaeration coefficient (k ₂) model for Atuwara River. Models that passed the confidence limit were subjected to model evaluation using measures of agreement between observed and predicted data such as percent bias, Nash–Sutcliffe efficiency, and root mean square observation standard deviation ratio. The used approach yield better results than empirical models developed for local conditions while it is also useful in conserving scarce resources.     

Multivariate analysis of potentially toxic metals in sediments of a tropical coastal lagoon

Surface sediments collected from the Lagos Lagoon, Nigeria, and three adjoining rivers were analysed for their physicochemical properties and pseudo-total concentration of the potentially toxic metals (PTM) Cd, Cr, Cu, Pb and Zn. The concentration of the PTM varied seasonally and spatially. Odo-Iyaalaro was observed to be the most polluted river, with highest concentrations of 42.1 mg kg^?1, 102 mg kg^?1, 185 mg kg^?1, 154 mg kg^?1 and 1040 mg kg^?1 of Cd, Cr, Cu, Pb and Zn, respectively, while Ibeshe River was the least contaminated, apart from a site affected by Cu from the textile industry. Some of the sediments were found to be above the consensus-based probable effect concentrations and Dutch sediment guideline for metals. Overall metal concentrations were similar to those reported for other tropical lagoon and estuarine systems affected by anthropogenic inputs as a result of rapid urbanisation. Due to the large number of samples, principal component analysis was used to examine relationships within the data set. Generally, sediments collected during the dry season were observed to have higher concentration of PTM than those collected during the rainy season. This means that PTM could accumulate over a prolonged period and then be released relatively rapidly, on an annual basis, into tropical lagoon systems.     

Effects of aqueous suspensions of titanium dioxide nanoparticles on Artemia salina: assessment of nanoparticle aggregation, accumulation, and toxicity

Aquatic stability and impact of titanium dioxide nanoparticles (TiO₂ NPs, 10–30 nm) were investigated using Artemia salina. Acute exposure was conducted on nauplii (larvae) and adults in seawater in a concentration range from 10 to 100 mg/L TiO₂ NPs for 24 and 96 h. Rapid aggregation occurred in all suspensions of TiO₂ NPs to form micrometer size particles. Yet, both nauplii and adults accumulated the aggregates significantly. Average TiO₂ content in nauplii ranged from 0.47 to 3.19 and from 1.29 to 4.43 mg/g in 24 and 96 h, respectively. Accumulation in adults was higher ranging from 2.30 to 4.19 and from 4.38 to 6.20 mg/g in 24 and 96 h, respectively. Phase contrast microscopy images revealed that Artemia were unable to excrete the particles. Thus, the TiO₂ aggregates filled inside the guts. No significant mortality or toxicity occurred within 24 h at any dose. Lipid peroxidation levels characterized with malondialdehyde concentrations were not statistically different from those of the controls (p?>?0.05). These results suggested that suspensions of the TiO₂ NPs were nontoxic to Artemia, most likely due to the formation of benign TiO₂ aggregates in water. In contrast, both mortality and lipid peroxidation increased in extended exposure to 96 h. Highest mortality occurred in 100 mg/L TiO₂ NP suspensions; 18 % for nauplii and 14 % for adults (LC₅₀?>?100 mg/L). These effects were attributed to the particle loading inside the guts leading to oxidative stress as a result of impaired food uptake for a long period of time.     

Characterization of microbial communities from coastal waters using microarrays

Molecular methods, including DNA probes, were used to identify and enumerate pathogenic Vibrio species in the Chesapeake Bay; our data indicated that Vibrio vulnificus exhibits seasonal fluctuations in number. Our work included a characterization of total microbial communities from the Bay; development of microarrays that identify and quantify the diversity of those communities; and observation of temporal changes in those communities. To identify members of the microbial community, we amplified the 16S rDNA gene from community DNA isolated from a biofilm sample collected from the Chesapeake Bay in February, 2000. The resultant 75 sequences were 95% or more similar to 7 species including two recently described Shewanella species, baltica and frigidimarina, that have not been previously isolated from the Chesapeake. When the genera of bacteria from biofilm after culturing are compared to those detected by subcloning amplified 16S fragments from community DNA, the cultured sample exhibited a strong bias. In oysters collected in February, the most common bacteria were previously unknown. Based on our 16S findings, we are developing microarrays to detect these and other microbial species in these estuarine communities. The microarrays will detect each species using four distinct loci, with the multiple loci serving as an internal control. The accuracy of the microarray will be measured using sentinel species such as Aeromonas species, Escherichia coli, and Vibrio vulnificus. Using microarrays, it should be possible to determine the annual fluctuations of bacterial species (culturable and non-culturable, pathogenic and non-pathogenic). The data may be applied to understanding patterns of environmental change; assessing the health of the Bay; and evaluating the risk of human illness associated with exposure to and ingestion of water and shellfish.     

First Jurassic Choristodera from Asia

Although choristoderes have a good Lower Cretaceous record in Asia, they have never previously been recorded from Jurassic deposits. Here we describe fragmentary vertebral material referable to Choristodera indet. from the Middle Jurassic Balabansai Svita of the Fergana Valley, Kyrgyzstan. This provides a significant range extension for the group in Asia and shows that choristoderes already had a Pan-Laurasian distribution in the Jurassic.     

The influence of source and timing of nitrogen fertilizers on yield and nitrogen use efficiency of four sweet potato cultivars

Nitrogen (N) availability is a very important determinant of crop yield. It is also one of the most expensive inputs in crop production. Thus, the efficient management of N by farmers with limited resource is a very important part of successful soil and crop management system. A field study was conducted on a Norfolk sandy loam soil at the George Washington Carver Agricultural Experiment Station, Tuskegee, AL, to evaluate the influence of fertilizer source and timing on the yield of four sweet potato [Ipomoea batatas (L.)] cultivars. Two N sources (urea, CO(NH₂)₂ and ammonium nitrate, NH₄NO₃), four sweet potato cultivars (‘Georgia Jet’, GA-Jet; ‘TU-82-155’, TU-155; ‘TU-1892’; and ‘Rojo Blanco’, Rojo-Bl) and three times (zero, single, and split applications) were used in a factorial designed experiment. Plants were harvested after 80 and 120 days and total and marketable yields determined. Nitrogen recovery efficiency, yield efficiency and physiological efficiency were also determined. Total and marketable yields of early maturing cultivars were significantly higher than of late maturing cultivars (P<0.05). The single application of N resulted in significantly higher yield in storage roots than split application (P<0.05). Physiological efficiency values were highly correlated with total marketable yields. Recovery rates increased with time. Late maturing cultivars tended to have higher N recovery and physiological efficiency than early maturing cultivars. These results suggest that cultivar maturity group should play an important part in N fertilization recommendations for sweet potato.