Use of principal component analysis to profile temporal and spatial variations of chlorinated solvent concentration in groundwater

This work aims at evaluating spatial distribution patterns of concentration variations for chlorinated solvents in groundwater, based on principal component analysis and geographic information system (GIS) tools. The study investigates long-time series of chlorinated solvent concentrations in groundwater measured for 18 contaminated industrial sites. The characterization of contaminant plumes and delineation of pollutant sources are essential for choosing appropriate monitoring and remediation strategies, as contaminated groundwaters are characterized by complex patterns of spatial and temporal concentration variability, with wide unpredictable fluctuations over time. The present work describes the results of a new exploratory statistical method called the Variability Index Method (VIM) applied to environmental data to assess the performance of using concentration variations as molecular tracers to reveal aquifer dynamics, industrial impacts, and point sources for contamination plumes. The application of this method provides a useful assessment of controls over contaminant concentration variations as well as support for remediation techniques.     

Particle fluxes above forests: observations, methodological considerations and method comparisons

This paper reports a study designed to test, evaluate and compare micro-meteorological methods for determining the particle number flux above forest canopies. Half-hour average particle number fluxes above a representative broad-leaved forest in Denmark derived using eddy covariance range from -7x10(7) m(-2) s(-1) (1st percentile) to 5x10(7) m(-2) s(-1) (99th percentile), and have a median value of -1.6x10(6) m(-2) s(-1). The statistical uncertainties associated with the particle number flux estimates are larger than those for momentum fluxes and imply that in this data set approximately half of the particle number fluxes are not statistically different to zero. Particle number fluxes from relaxed eddy accumulation (REA) and eddy covariance are highly correlated and of almost identical magnitude. Flux estimates from the co-spectral and dissipation methods are also correlated with those from eddy covariance but exhibit higher absolute magnitude of fluxes.     

Influence of natural dissolved organic carbon on the bioavailability of mercury to a freshwater alga

Bioavailability of mercury (Hg) to Selenastrum capricornutum was assessed in bioassays containing field-collected freshwater of varying dissolved organic carbon (DOC) concentrations. Bioconcentration factor (BCF) was measured using stable isotopes of methylmercury (MeHg) and inorganic Hg(II). BCFs for MeHg in low-DOC lake water were significantly larger than those in mixtures of lake water and high-DOC river water. The BCF for MeHg in rainwater (lowest DOC) was the largest of any treatment. Rainwater and lake water also had larger BCFs for Hg(II) than river water. Moreover, in freshwater collected from several US and Canadian field sites, BCFs for Hg(II) and MeHg were low when DOC concentrations were >5mg L(-1). These results suggest high concentrations of DOC inhibit bioavailability, while low concentrations may provide optimal conditions for algal uptake of Hg. However, variability of BCFs at low DOC indicates that DOC composition or other ligands may determine site-specific bioavailability of Hg.     

Correlates of mercury in fish from lakes near Clyde Forks, Ontario, Canada

Subsurface soils near Clyde Forks, Ontario, Canada, can have naturally high concentrations of mercury (Hg) from local geological sources. To investigate Hg in local aquatic food webs, Hg was measured in fish dorsal muscle (mainly yellow perch [YP] and pumpkinseed sunfish [PS]) and surface sediments from 10 regional lakes. Water chemistry, along with fork length, weight, and stable isotopes (delta15N, delta13C, delta34S) in fish were also measured. No lake sediments had elevated (>0.3microg/g dw) Hg, and average Hg concentrations in fish were not sufficiently high (<1microg/g dw) to be of concern for fish-eating wildlife. Variance in fish Hg was best explained by dietary carbon source (delta13C), and certain lake variables (e.g., pH for YP). PS with more pelagic feeding habits had higher delta34S and Hg than those with more littoral feeding habits. Potential biological linkages between fish Hg and delta34S, a parameter that may be related to the lake sulphate-reducing bacteria activity, requires further investigation.     

Modulation of steroidogenesis by coastal waters and sewage effluents of Hong Kong, China, using the H295R assay

BACKGROUND, AIM, AND SCOPE: The presence of a variety of pollutants in the aquatic environment that can potentially interfere with the production of sex steroid hormones in wildlife and humans has been of increasing concern. The aim of the present study was to investigate the effects of extracts from Hong Kong marine waters, and influents and effluents from wastewater treatment plants on steroidogenesis using the H295R cell bioassay. After exposing H295R cells to extracts of water, the expression of four steroidogenic genes and the production of three steroid hormones were measured. MATERIALS AND METHODS: Water samples were collected during the summer of 2005 from 24 coastal marine areas and from the influents and effluents of two major waste water treatment plants (WWTPs) in Hong Kong, China. Samples were extracted by solid phase extraction (SPE). H295R cells were exposed for 48 h to dilutions of these extracts. Modulations of the expression of the steroidogenic genes CYP19, CYP17, 3betaHSD2, and CYP11beta2 were determined by measuring mRNA concentrations by real-time polymerase chain reaction (Q-RT-PCR). Production of the hormones progesterone (P), estradiol (E2), and testosterone (T) was quantified using enzyme linked immunosorbent assays (ELISA). RESULTS: Extracts from samples collected in two fish culture areas inhibited growth and proliferation of H295R cells at concentrations greater or equal to 10(5) L equivalents. The cells were exposed to the equivalent concentration of active substances in 10,000 L of water. Thus, to observe the same level of effect as observed in vitro on aquatic organisms would require a bioaccumulation factor of this same magnitude. None of the other 22 marine samples affected growth of the cells at any dilution tested. Twelve of the marine water samples completely inhibited the expression of CYP19 without affecting E2 production; inhibition of CYP17 expression was observed only in one of the samples while expression of CYP11beta2 was induced as much as five- and ninefold after exposure of cells to extracts from two locations. The expression of the progesterone gene 3betaHSD2 was not affected by any of the samples; only one sample induced approximately fourfold the production of E2. Although more than twofold inductions were observed for P and T production, none of these values were statistically significant to conclude effects on the production of these two hormones. While influents from WWTPs did not affect gene expression, an approximately 30% inhibition in the production of E2 and a 40% increase in P occurred for the exposure with influents from the Sha Tin and Stonecutters WWTPs, respectively. Effluents from WWTPs did not affect the production of any of the studied hormones, but a decrement in the expression of the aldosterone gene CYP11beta2 was observed for the Sha Tin WWTP exposure. No direct correlation could be established between gene expression and hormone production. DISCUSSION: Observed cytotoxicity in the two samples from fish culture areas suggest the presence of toxic compounds; chemical analysis is required for their full identification. Although effluents from WWTPs did not affect hormone production, other types of endocrine activity such as receptor-mediated effects cannot be ruled out. Interactions due to the complexity of the samples and alternative steroidogenic pathways might explain the lack of correlation between gene expression and hormone production results. CONCLUSIONS: Changes observed in gene expression and hormone production suggest the presence in Hong Kong coastal waters of pollutants with endocrine disruption potential and others of significant toxic effects. The aromatase and aldosterone genes seem to be the most affected by the exposures, while E2 and P are the hormones with more significant changes observed. Results also suggest effectiveness in the removing of compounds with endocrine activity by the WWTPs studied, as effluent samples did not significantly affect hormone production. The H295R cell showed to be a valuable toll in the battery required for the analysis of endocrine disrupting activities of complex environmental samples. RECOMMENDATIONS AND PERSPECTIVES: Due to the intrinsic complexity of environmental samples, a combination of analytical tools is required to realistically assess environmental conditions, especially in aquatic systems. In the evaluation of endocrine disrupting activities, the H295R cell bioassay should be used in combination with other genomic, biological, chemical, and hydrological tests to establish viable modes for endocrine disruption and identify compounds responsible for the observed effects.     

Levels of perfluorochemicals in water samples from Catalonia,Spain: is drinking water a significant contribution to human exposure?

Background, aim, and scope  In recent years, due to a high persistence, biomagnification in food webs, presence in remote regions, and potential toxicity, perfluorochemicals (PFCs) have generated a considerable interest. The present study was aimed to determine the levels of perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), and other PFCs in drinking water (tap and bottled) and river water samples from Tarragona Province (Catalonia, Spain). Materials and methods  Municipal drinking (tap) water samples were collected from the four most populated towns in the Tarragona Province, whereas samples of bottled waters were purchased from supermarkets. River water samples were collected from the Ebro (two samples), Cortiella, and Francolí Rivers. After pretreatment, PFC analyses were performed by HPLC-MS. Quantification was done using the internal standard method, with recoveries between 68% and 118%. Results  In tap water, PFOS and PFOA levels ranged between 0.39 and 0.87 ng/L (0.78 and 1.74 pmol/L) and between 0.32 and 6.28 ng/L (0.77 and 15.2 pmol/L), respectively. PFHpA, PFHxS, and PFNA were also other detected PFCs. PFC levels were notably lower in bottled water, where PFOS could not be detected in any sample. Moreover, PFHpA, PFHxS, PFOA, PFNA, PFOS, PFOSA, and PFDA could be detected in the river water samples. PFOS and PFOA concentrations were between <0.24 and 5.88 ng/L (<0.48 and 11.8 pmol/L) and between <0.22 and 24.9 ng/L (<0.53 and 60.1 pmol/L), respectively. Discussion  Assuming a human water consumption of 2 L per day, the daily intake of PFOS and PFOA by the population of the area under evaluation was calculated (0.78–1.74 and 12.6 ng, respectively). It was found that drinking water might be a source of exposure to PFCs as important as the dietary intake of these pollutants. Conclusions  The contribution of drinking water (tap and bottled) to the human daily intake of various PFCs has been compared for the first time with data from dietary intake of these PFCs. It was noted that in certain cases, drinking water can be a source of exposure to PFCs as important as the dietary intake of these pollutants although the current concentrations were similar or lower than those reported in the literature for surface water samples from a number of regions and countries. Recommendations and perspectives  Further studies should be carried out in order to increase the knowledge of the role of drinking water in human exposure to PFCs.     

Acute toxic hazard evaluations of glyphosate herbicide on terrestrial vertebrates of the oregon coast range

GOAL, SCOPE AND BACKGROUND: The degree to which dose responses of model organisms (lab rodents) can adequately predict dose responses of free-ranging wild mammals or amphibians is unknown, and the relative sensitivity of such species to body loading of a toxicant such as glyphosate is seldom reported. For relative effects of dosage, we compare sensitivity of nine wild vertebrate species to effects of high doses of glyphosate in Swiss-Webster laboratory mice both by gavage and by intraperitoneal injection. We also evaluate sublethal effects of herbicide exposure on behavior and reproductive success of one mammal and one amphibian species. METHODS: Comparisons of acute toxicity of glyphosate were made with intraperitoneal dosings of technical glyphosate isopropylamine salt to nine species of terrestrial vertebrates (five amphibians, four mammals) and compared with responses in Swiss-Webster laboratory mice. Animals collected from sites that had no recent herbicide application were allowed 7-14 days to equilibrate in captivity before treatment. RESULTS: Median lethal dose ranged from 800 to 1,340 mg kg(-1) in mammals, and 1,170 to >2,000 mg kg(-1) in amphibians, with Oregon vole being the most sensitive. White lab mice were in the middle of the mammalian range. Tailed frog, at >2,000 mg kg(-1) was the least sensitive. Calibration of IP sensitivity to oral administration by gavage indicated that roughly four times as much glyphosate must be administered to obtain a comparable estimate of lethality. Administration by gavage in highly concentrated solutions tended to cause physical injury, hence may prove less useful as a relative indicator of toxicity. When sublethal dosages were given to roughskin newts or chipmunks, mobility and use of cover appeared largely unaffected. DISCUSSION: Direct toxic effects of spraying glyphosate under normal forest management seem unlikely for the nine species examined. Nor could we detect significant indirect effects of exposure on behavior and use of cover features in two species. There may be effects on other aspects of the field biology of these animals, such as reproductive rates, which we did not investigate. Recent field data indicate that changes in habitat quality following herbicide application can result in high reproductive activity in species associated with the grasses and forbs that proliferate following field applications. CONCLUSIONS: When compared to field data on body burdens of wild mammals exposed after aerial application of glyphosate at maximum rates in forests, there seems to be a large margin of safety between dosages encountered and those causing either death or limitation of movement, foraging or shelter. RECOMMENDATIONS AND PERSPECTIVES: Margins of safety for small mammals and amphibians appear to be large under any probable exposure scenarios, however our results indicate high variability in responses among species. Uncertainty introduced into field studies from unknown sources of mortality (e.g, likely predation) must be considered when interpreting our results.     

Functionally relevant microorganisms to enhanced biological phosphorus removal performance at full-scale wastewater treatment plants in the United States

The abundance and relevance ofAccumulibacter phosphatis (presumed to be polyphosphate-accumulating organisms [PAOs]), Competibacter phosphatis (presumed to be glycogen-accumulating organisms [GAOs]), and tetrad-forming organisms (TFOs) to phosphorus removal performance at six full-scale enhanced biological phosphorus removal (EBPR) wastewater treatment plants were investigated. Coexistence of various levels of candidate PAOs and GAOs were found at these facilities. Accumulibacter were found to be 5 to 20% of the total bacterial population, and Competibacter were 0 to 20% of the total bacteria population. The TFO abundance varied from nondetectable to dominant. Anaerobic phosphorus (P) release to acetate uptake ratios (P(rel)/HAc(up)) obtained from bench tests were correlated positively with the abundance ratio of Accumulibacter/(Competibacter +TFOs) and negatively with the abundance of (Competibacter +TFOs) for all plants except one, suggesting the relevance of these candidate organisms to EBPR processes. However, effluent phosphorus concentration, amount of phosphorus removed, and process stability in an EBPR system were not directly related to high PAO abundance or mutually exclusive with a high GAO fraction. The plant that had the lowest average effluent phosphorus and highest stability rating had the lowest P(rel)/HAc(up) and the most TFOs. Evaluation of full-scale EBPR performance data indicated that low effluent phosphorus concentration and high process stability are positively correlated with the influent readily biodegradable chemical oxygen demand-to-phosphorus ratio. A system-level carbon-distribution-based conceptual model is proposed for capturing the dynamic competition between PAOs and GAOs and their effect on an EBPR process, and the results from this study seem to support the model hypothesis.     

Preparation of a porous clay heterostructure and study of its adsorption capacity of phenol and chlorinated phenols from aqueous solutions.

A porous clay heterostructure (PCH) from a Mexican clay was prepared and characterized, and its aqueous phenol and dichlorophenols (DCPs) adsorption capacities were studied using a batch equilibrium technique. The PCH displayed a surface area of 305.5 m2/g, 37.2 A average porous diameter, and a basal space of 23.2 A. The adsorption capacity shown by the PCH for both phenol and DCPs from water (14.5 mg/g for phenol; 48.7 mg/g for 3,4-DCP; and 45.5 mg/g for 2,5-DCP) suggests that the PCH has both hydrophobic and hydrophilic characteristics, as a result of the presence of silanol and siloxane groups formed during the pillaring and calcination of the PCH. The values of maximal adsorption capacity for dichlorophenols were higher than those reported for aluminum pillared clays and some inorgano-organo clays and comparable with some ionic exchange resins.     

Phosphorus removal from municipal wastewater by hydrous ferric oxide reactive filtration and coupled chemically enhanced secondary treatment: part I--performance.

This work examines the performance of a hydrous ferric oxide (HFO) reactive filtration (RF) process with coupled chemically enhanced secondary treatment (RECYCLE) for phosphorus removal from municipal wastewater (HFO-RF-RECYCLE). A 3-month, 0.95-ML/d (0.25-mgd) demonstration of HFO-RF-RECYCLE was performed at a municipal wastewater treatment plant equipped with oxidation ditches and secondary clarifiers. Influent to the plant averaged 6.0 mg/L phosphorus, with a tertiary effluent average of 0.011 mg/L phosphorus. Iron doses to the plant were low, at 5 mg/L. Inline recycling of HFO solution rejects to the plant influent resulted in a maximum 90.3%, dose-dependent reduction of phosphorus in the secondary effluent at 4.5 ML/d (1.2 mgd). Other results included reduction of total suspended solids and turbidity. A mass balance analysis was performed. We conclude that HFO-RF-RECYCLE may allow very low levels of phosphorus discharge from municipal wastewater treatment plants with a ferric-iron-based tertiary filtration process and residual recycling.