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.     

Arsenic and other trace elements in two catfish species from Paranaguá Estuarine Complex, Paraná, Brazil

Concentrations of arsenic and four additional trace elements (Cu, Cr, Ni, and Zn) were determined by inductively coupled plasma–optical emission spectrometry in the muscular tissue of the yellow catfish (Cathorops spixii) and the urutu catfish (Genidens genidens) from Paranaguá Estuarine Complex, Brazil (PEC). The PEC can be characterized by an environment of high ecological and economic importance in which preserved areas of rainforest and mangroves coexist with urban activities as ports and industries. The average concentrations (in milligram per kilogram dry weight) of elements in the muscle tissue of C. spixii are as follows: Zn (31), As (17), Cu (1.17), Cr (0.62), and Ni (0.28). Similar concentrations could be found in G. genidens with exception of As: Zn (36), As (4.78), Cu (1.14), Cr (0.51), and Ni (0.14). Fish from the geographic northern rural region (Guaraqueçaba–Benito) display higher As concentrations in the muscle tissues than fish found in the south-western (urban) part of the PEC. An international comparison of muscle tissue concentrations of trace elements in fish was made. Except for Ni in C. spixii, a tendency of decrease in element concentration with increasing size (age) of the fish could be observed. According to the National Health Surveillance Agency of Brazil, levels of Cr and As exceeded the permissible limits for seafood. An estimation of the provisional tolerable weekly intake of As was calculated with 109 % for C. spixii and with 29 % for G. genidens.     

On-line dechlorination–hydrogenation of chlorinated paraffin mixtures using GC and GC/MS

Chlorinated paraffins (CPs) are straight chain hydrocarbons that are produced as complex mixtures and are used as flame retardants and paint additives. These mixtures are extremely difficult to characterize using conventional chromatographic methods, as conventional gas chromatography results in unresolved complex chromatograms that preclude the identification and quantification of individual congeners or any reasonable assessment of the average carbon chain length. Carbon chain length is an important parameter for assessing physical properties and the toxicity of these materials. We have modified and improved a previously published gas chromatography–flame ionization detector method that uses Pd catalyst held in the gas chromatograph injector to simultaneously dechlorinate the CPs and separate the resulting alkanes. In addition, we have adapted this method to gas chromatography–mass spectrometry. Dehalogenation of other compounds was also studied with this system to investigate potential application to other complex halogenated mixtures.     

Hepatic mercury,cadmium, and lead in mink and otter from New York State: monitoring environmental contamination

Many non-linear processes link atmospheric emissions to the bioavailability of metals; consequently, the monitoring of metals in ecosystem components is required to model their ecodynamics. American mink (Neovison vison) and river otter (Lontra canadensis) have the potential to serve as an upper-level-consumer component in monitoring metals bioavailability. However, the relationship of bioaccumulated metals to various environmental factors has not been explored nor have the effects of demographic factors been resolved. To address these limitations, mink and otter, collected throughout New York State during 1998–2002, were analyzed for hepatic concentrations of total mercury (Hg), cadmium (Cd), and lead (Pb). Relationships were investigated between metals concentrations and landscape-level factors (physiographic zone, hydrologic unit, and elevation) and demographic factors (gender and age). Considerable variation in Hg and Cd concentrations was observed relative to both physiographic zone and hydrologic unit for both species. In contrast with Hg, Cd concentration increased predictably with increasing elevation. Mercury concentrations were greater, but for Cd less, in otter than mink. Lead concentrations showed little landscape heterogeneity and were independent of elevation. Age-related bioaccumulation was evident for Hg and Cd, but not for Pb, in both species. Mercury and Cd concentrations were greater in female than male mink; however, Pb concentrations were greater in males than females. Inverse relationships of relative growth (weight/length) to metals concentrations explained gender differences in Hg and Cd in mink. For otter, no gender-related differences in metals concentrations were apparent. The suitability of mink and otter for monitoring programs is discussed.     

A study of the effect of physical and chemical stressors on biological integrity within the San Diego hydrologic region

Environmental agencies across the United States have searched for adequate methods to assess anthropogenic impacts on the environment. Biological assessments, which compare the taxonomic composition of an aquatic assemblage to relevant biocriteria, have surfaced as an effective method to assess the ecological integrity of US waterbodies. In this study, bioassessment data were collected and analyzed in conjunction with physical habitat and chemical stressor data for streams and rivers within the San Diego basin from 1998 through 2005. Physical stressors such as sediment loading, riparian destruction, and in-stream habitat homogenization affect many locations in the region. However, physical habitat measures alone were found to frequently overestimate the biological integrity of streams in the region. Many sites within the San Diego Basin, although unaffected by physical stressors, continue to exhibit low biological integrity scores. Sites with low biological integrity tend to possess higher specific conductance and salinity compared to sites with high biological integrity. We suggest that one possible reason for these differences is the source water used for municipal purposes.     

Assessment of Spatiotemporal Varying Relationships Between Rainfall,Land Cover and Surface Water Area Using Geographically Weighted Regression

Traditional regression techniques such as ordinary least squares (OLS) are often unable to accurately model spatially varying data and may ignore or hide local variations in model coefficients. A relatively new technique, geographically weighted regression (GWR) has been shown to greatly improve model performance compared to OLS in terms of higher R ² and lower corrected Akaike information criterion (AIC_C). GWR models have the potential to improve reliabilities of the identified relationships by reducing spatial autocorrelations and by accounting for local variations and spatial non-stationarity between dependent and independent variables. In this study, GWR was used to examine the relationship between land cover, rainfall and surface water habitat in 149 sub-catchments in a predominately agricultural region covering 2.6 million ha in southeast Australia. The application of the GWR models revealed that the relationships between land cover, rainfall and surface water habitat display significant spatial non-stationarity. GWR showed improvements over analogous OLS models in terms of higher R ² and lower AIC_C. The increased explanatory power of GWR was confirmed by the results of an approximate likelihood ratio test, which showed statistically significant improvements over analogous OLS models. The models suggest that the amount of surface water area in the landscape is related to anthropogenic drainage practices enhancing runoff to facilitate intensive agriculture and increased plantation forestry. However, with some key variables not present in our analysis, the strength of this relationship could not be qualified. GWR techniques have the potential to serve as a useful tool for environmental research and management across a broad range of scales for the investigation of spatially varying relationships.     

Changes in the sorption and rate of 17β-estradiol biodegradation by dissolved organic matter collected from different water sources

The potential biodegradation and subsequent transformation of 17β-estradiol (E2) to estrone (E1) were examined in the presence of various dissolved organic matter (DOM) isolated from effluent, river and lake waters. In addition, estrogenicity was estimated in association with the removal of E2 via its sorption onto DOM and biodegradation. The more biodegradable lake-derived DOM promoted more extensive transformation of E2 into E1 than the effluent organic matter through a biodegradation process. Overall, under all conditions, biodegradation dominated the removal of E2 in water. The increased dissolved organic carbon (DOC) concentrations in river and lake-derived DOM (e.g. 6.5 mg C L(-1)) reduced the removal of E2 by decreasing its biodegradation due to the moderate sorption of E2 onto DOM. The effluent organic matter showed greater removal of E2 via biodegradation, as well as significantly high sorption. This was associated with a large amount of hydrophobic fulvic acid (FA)- and humic acid (HA)-like organic components, as shown by the small increase in the specific UV absorbance at 254 nm (SUVA(254)). An increase in the DOC concentration reduced the removal of E2, resulting in high estrogenicity. The present study suggests that both organic composition and DOC concentration influenced the removal of E2 and, therefore, should be fully considered when assessing estrogenicity and its impacts on the aquatic environment.