A directional passive air sampler for monitoring polycyclic aromatic hydrocarbons (PAHs) in air mass

A passive air sampler was developed for collecting polycyclic aromatic hydrocarbons (PAHs) in air mass from various directions. The airflow velocity within the sampler was assessed for its responses to ambient wind speed and direction. The sampler was examined for trapped particles, evaluated quantitatively for influence of airflow velocity and temperature on PAH uptake, examined for PAH uptake kinetics, calibrated against active sampling, and finally tested in the field. The airflow volume passing the sampler was linearly proportional to ambient wind speed and sensitive to wind direction. The uptake rate for an individual PAH was a function of airflow velocity, temperature and the octanol-air partitioning coefficient of the PAH. For all PAHs with more than two rings, the passive sampler operated in a linear uptake phase for three weeks. Different PAH concentrations were obtained in air masses from different directions in the field test.     

Kinetic extractions to assess mobilization of Zn, Pb, Cu, and Cd in a metal-contaminated soil: EDTA vs. citrate

Kinetic EDTA and citrate extractions were used to mimic metal mobilization in a soil contaminated by metallurgical fallout. Modeling of metal removal rates vs. time distinguished two metal pools: readily labile (QM1) and less labile (QM2). In citrate extractions, total extractability (QM1+QM2) of Zn and Cd was proportionally higher than for Pb and Cu. Proportions of Pb and Cu extracted with EDTA were three times higher than when using citrate. We observed similar QM1/QM2 ratios for Zn and Cu regardless of the extractant, suggesting comparable binding energies to soil constituents. However, for Pb and Cd, more heterogeneous binding energies were hypothesized to explain different kinetic extraction behaviors. Proportions of citrate-labile metals were found consistent with their short-term, in-situ mobility assessed in the studied soil, i.e., metal amount released in the soil solution or extracted by cultivated plants. Kinetic EDTA extractions were hypothesized to be more predictive for long-term metal migration with depth.     

Monitoring contaminants from oil production at sea by measuring gill EROD activity in Atlantic cod (Gadus morhua)

An ex vivo gill EROD assay was applied in Atlantic cod (Gadus morhua) as a biomarker for waterborne CYP1A-inducing compounds derived from oil production at sea. Exposure to nominal concentrations of 1 ppm or 10 ppm North Sea crude oil in a static water system for 24 h caused a concentration-dependent gill EROD induction. Further, exposure of cod for 14 days to environmentally relevant concentrations of produced water (PW, diluted 1:200 or 1:1000) from a platform in the North Sea using a flow-through system resulted in a concentration-dependent induction of gill EROD. Crude oil (0.2 ppm) from the same oil field also proved to induce EROD. Finally, gill EROD activity in cod caged for 6 weeks at 500-10 000 m from two platforms outside Norway was measured. The activities in these fish were very low and did not differ from those in fish caged at reference sites.     

In field arsenic removal from natural water by zero-valent iron assisted by solar radiation

An in situ arsenic removal method applicable to highly contaminated water is presented. The method is based in the use of steel wool, lemon juice and solar radiation. The method was evaluated using water from the Camarones River, Atacama Desert in northern Chile, in which the arsenic concentration ranges between 1000 and 1300 μg L⁻¹. Response surface method analysis was used to optimize the amount of zero-valent iron (steel wool) and the citrate concentration (lemon juice) to be used. The optimal conditions when using solar radiation to remove arsenic from natural water from the Camarones river are: 1.3 g L⁻¹ of steel wool and one drop (ca. 0.04 mL) of lemon juice. Under these conditions, removal percentages are higher than 99.5% and the final arsenic concentration is below 10 μg L⁻¹. This highly effective arsenic removal method is easy to use and inexpensive to implement.     

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.     

Implications of urine-to-feces ratio in the thermophilic anaerobic digestion of swine waste.

Thermophilic anaerobic digestion of swine manure represents a potential waste treatment technology to address environmental concerns, such as odor emissions and removal of pathogenic microorganisms. However, there are concerns relative to the stability of this process when swine manure is the sole substrate. In this study, the potential of biogas production from swine manure as the sole substrate under thermophilic (50 degrees C) conditions was investigated in the laboratory, to determine whether separation of urine and feces as part of the waste collection process would benefit anaerobic digestion. Effluent from a continuously stirred tank reactor was used as the inoculum for batch tests, in which the substrate contained three different concentrations of urine (urine-free, as-excreted urine-to-feces ratio and double the as-excreted urine-to-feces ratio). Inocula were acclimated to these same urine-to-feces ratios to determine methane production. Results show that both urine-free and as-excreted substrates were not inhibitory to anaerobic inocula. Anaerobic microorganisms can be readily acclimated to substrate with double the as-excreted urine concentration, which contained nitrogen concentrations up to 7.20 g/L. Cumulative methane production reached similar levels in the batch tests, regardless of the substrate urine concentration.     

Techniques for the stabilization and assessment of treated copper-, chromium-, and arsenic-contaminated soil

Remediation mainly based on excavation and burial of the contaminated soil is impractical with regard to the large numbers of sites identified as being in need of remediation. Therefore, alternative methods are needed for brownfield remediation. This study was conducted to assess a chemical stabilization procedure of CCA-contaminated soil using iron (Fe)-containing blaster sand (BS) or oxygen-scarfing granulate (OSG). The stabilization technique was assessed with regard to the feasibility of mixing ameliorants at an industrial scale and the efficiency of the stabilization under different redox conditions. The stability was investigated under natural conditions in 1-m3 lysimeters in a field experiment, and the effect of redox conditions was assessed in a laboratory experiment (10 L). The treatments with high additions of ameliorant (8% and 17%) were more successful in both the laboratory and field experiments, even though there was enough Fe on a stochiometric basis even at the lowest addition rates (0.1% and 1%). The particle size of the Fe and the mixing influenced the stabilization efficiency. The development of anaerobic conditions, simulated by water saturation, increases the fraction of arsenic (AsIII) and, consequently, As mobility. The use of high concentrations of OSG under aerobic conditions increased the concentrations of nickel (Ni) and copper (Cu) in the pore water. However, under anaerobic conditions, it decreased the As leaching compared with the untreated soil, and Ni and Cu leaching was not critical. The final destination of the treated soil should govern the amendment choice, that is, an OSG concentration of approximately 10% may be suitable if the soil is to be landfilled under anaerobic conditions. Alternatively, the soil mixed with 1% BS could be kept under aerobic conditions in a landfill cover or in situ at a brownfield site. In addition, the treatment with BS appeared to produce better effects in the long term than treatment with OSG.     

Net methylmercury production as a basis for improved risk assessment of mercury-contaminated sediments

Sediments contaminated by various sources of mercury (Hg) were studied at 8 sites in Sweden covering wide ranges of climate, salinity, and sediment types. At all sites, biota (plankton, sediment living organisms, and fish) showed enhanced concentrations of Hg relative to corresponding organisms at nearby reference sites. The key process determining the risk at these sites is the net transformation of inorganic Hg to the highly toxic and bioavailable methylmercury (MeHg). Accordingly, Hg concentrations in Perca fluviatilis were more strongly correlated to MeHg (p < 0.05) than to inorganic Hg concentrations in the sediments. At all sites, except one, concentrations of inorganic Hg (2-55 microg g(-1)) in sediments were significantly, positively correlated to the concentration of MeHg (4-90 ng g(-1)). The MeHg/Hg ratio (which is assumed to reflect the net production of MeHg normalized to the Hg concentration) varied widely among sites. The highest MeHg/Hg ratios were encountered in loose-fiber sediments situated in southern freshwaters, and the lowest ratios were found in brackish-water sediments and firm, minerogenic sediments at the northernmost freshwater site. This pattern may be explained by an increased MeHg production by methylating bacteria with increasing temperature, availability of energy-rich organic matter (which is correlated with primary production), and availability of neutral Hg sulfides in the sediment pore waters. These factors therefore need to be considered when the risk associated with Hg-contaminated sediments is assessed.     

Fluorescence fingerprints and Cu2+-complexing ability of individual molecular size fractions in soil- and waste-borne DOM

Land spreading of organic materials introduces large amounts of dissolved organic matter (DOM) into the soil. DOM has the ability to form stable complexes with heavy metals and can facilitate their transport towards the groundwater. The effects on soil processes are difficult to assess, because different DOM components might react differently towards metal ions. The objective of this study was to investigate the fluorescence signature and the Cu2+-binding capacity of individual molecular size fractions of DOM from various sources. DOM extracted from leaf compost, chicken manure, sugar cane vinasse and a fulvic hypercalcaric cambisol was fractionated by the means of dialysis into four molecular size classes: MW<500, 50012000-14000 Da. Vinasse and leaf compost contained around 80% and 70%, respectively, of the total organic carbon in the fractions with low molecular weight (MW<3500 Da); in chicken manure and soil these fractions accounted for 40% and 50% only. Fluorescence was highest in the fraction MW>12000 Da for leaf compost, chicken manure and soil. The opposite result was obtained for vinasse, where the fractions with low molecular weight showed highest fluorescence intensities, distinguishing it from all other samples. Vinasse showed the greatest ability to bind Cu2+ with a resulting complex concentration of 6.31mgl(-1) while in contact with an excess of Cu2+. Leaf compost, soil and chicken manure followed with 2.69, 1.12, and 0.85mgl(-1), respectively. Within vinasse, the fraction MW<500 Da was able to form the most DOM-Cu complexes, indicating the importance of low molecular weight fractions in metal binding.