Acute and reproductive toxicity of nano-sized metal oxides (ZnO and TiO₂) to earthworms (Eisenia fetida)

An increase in nanomaterial applications will likely lead to an increased probability of environmental exposures, raising concerns regarding the safety of these materials. Recent studies have indicated that manufactured nanomaterials, such as metal oxides, have the potential to be harmful to aquatic and terrestrial organisms. The majority of nano-metal oxide research addressing potential toxicological issues has been focused in aquatic environments with very little terrestrial data. This study characterized the acute and reproductive toxicity of zinc oxide (ZnO) and titanium dioxide (TiO(2)) to earthworms (Eisenia fetida) in a terrestrial system. Following a 14 d exposure, nano-sized ZnO on filter paper was acutely toxic to E. fetida, while nano-sized TiO(2) did not exhibit acute toxicity. In contrast, neither nano-sized ZnO nor TiO(2) exhibited acute toxicity to earthworms in sand. Both nano-sized ZnO and TiO(2), following a 4 week exposure, caused reproductive effects in earthworms in artificial soil. Overall, nano-sized ZnO exhibited greater toxicity than nano-sized TiO(2) in Eisenia fetida.     

Relationship between CH₄ and N₂O flux from soil and their ambient mixing ratio in a riparian rice-based agroecosystem of tropical region

Temporal variations of the ambient mixing ratio of greenhouse gas (CH(4) and N(2)O) in a riparian rice-based agro-ecosystem of tropical region were studied during 2005-2006 in coastal Odisha. The endeavour was made with the hypothesis that the ambient mixing ratio of CH(4) and N(2)O depends on the changes in the flux of CH(4) and N(2)O from the rice fields in the riparian rice ecosystems. A higher ambient mixing ratio of CH(4) was recorded during the tillering to grain filling stages of the rice crop, during both dry and wet seasons. The higher ambient mixing ratio of CH(4) during the wet season may attribute to the higher CH(4) emission from the rice field. The average mixing ratio of CH(4) was recorded as 1.84 ± 0.05 ppmv and 1.85 ± 0.06 ppmv during 2005 and 2006, respectively. The ambient CH(4) mixing ratio was recorded negatively correlated with the average ambient temperature. The N(2)O mixing ratio ranged from 261.57 to 399.44 ppbv with an average of 330.57 ppbv during 2005. However, the average mixing ratio of N(2)O was recorded as 318.83 ± 20.00 ppbv during 2006. The N(2)O mixing ratio was recorded to be negatively correlated with rainfall and average ambient temperature. Significant negative correlation (r = -0.209) of N(2)O with sunshine hours may attribute to the photochemical break down of N(2)O. The temporal variation of N(2)O flux from the rice field does not affect the ambient mixing ratio of N(2)O in the same way as in the case of the ambient mixing ratio of CH(4). However, the higher mixing ratio of N(2)O during the fallow period of the post monsoon period may attribute to the N(2)O flux from soil. Results indicate that intensively cultivated coastal ecosystems can be a major source of ambient greenhouse gas.     

A feeding inhibition based prediction of the toxic effect of dissolved metal mixtures upon Echinogammarus marinus (Crustacea: Amphipoda) at field relevant concentrations across a latitudinal gradient

Risk assessment of metals in the environment is performed mainly with toxicity evaluations on single metals, which is largely inadequate since these substances occur in mixtures. The development of models predicting combined toxic effects on the basis of the concentration-response relationships of individual compounds has emerged as an answer. In the present study, metal effects on post-exposure anorexia (the concept of FdC(50)--concentration causing 50% of feeding inhibition--is implemented) in Echinogammarus marinus, a widely distributed gammarid amphipod, were assessed and compared with modelled ones obtained through the application of the concentration addition (CA) model, which represents a reasonable worst-case scenario for the risk assessment of metal mixtures. Data were validated using in situ experiments performed along a latitudinal gradient (Iceland, Scotland and Portugal) aiming at establishing a geographic profile of autochthonous population susceptibilities to metals. For all of the metals studied concentrations in the water column at exposure sites were in good agreement with feeding inhibition levels. Models gave low to relatively high percentage agreement between predictions and experimental data. Boreal populations demonstrated higher susceptibility to single metals, but not to mixture exposures. Meridional populations denoted lower susceptibilities with higher FdC(50).     

Forensic fingerprinting and source identification of the 2009 Sarnia (Ontario) oil spill

This paper presents a case study in which integrated forensic oil fingerprinting and data interpretation techniques were used to characterize the chemical compositions and determine the source of the 2009 Sarnia (Ontario) oil spill incident. The diagnostic fingerprinting techniques include determination of hydrocarbon groups and semi-quantitative product-type screening via gas chromatography (GC), analysis of oil-characteristic biomarkers and the extended suite of parent and alkylated PAH (polycyclic aromatic hydrocarbon) homologous series via gas chromatography-mass spectrometry (GC-MS), determination and comparison of a variety of diagnostic ratios of "source-specific marker" compounds, and determination of the weathering degree of the spilled oil, and whether the spilled oil hydrocarbons have been mixed with any other "background" chemicals (biogenic and/or pyrogenic hydrocarbons). The detailed chemical fingerprinting data and results reveal the following: (1) all four samples are mixtures of diesel and lubricating oil with varying percentages of diesel to lube oil. Both samples 1460 and 1462 are majority diesel-range oil mixed with a smaller portion of lube oil. Sample 1461 contains slightly less diesel-range oil. Sample 1463 is majority lubricating-range oil. (2) The diesel in the four diesel/lube oil mixture samples was most likely the same diesel and from the same source. (3) The spill sample 1460 and the suspected-source sample 1462 have nearly identical concentrations and distribution patterns of target analytes including TPHs, n-alkane, PAHs and biomarker compounds; and have nearly identical diagnostic ratios of target compounds as well. Furthermore, a perfect "positive match" correlation line (with all normalized ratio data points falling into the straight correlation line) is clearly demonstrated. It is concluded that the spill oil water sample 1460 (#1, from the water around the vessel enclosed by a boom) matches with the suspected source sample 1462 (#3, from the vessel engine room bilge pump). (4) From the n-alkane and PAH analysis, it appears that the oil in the spill sample 1460 is slightly more weathered in comparison with sample 1462. The minor differences in fingerprints of two samples were most likely caused by weathering effects. (5) Sample 1461 (#2, from the vessel engine room bilge) and sample 1463 (#4, from the vessel bilge waste collection tank) demonstrated significantly different fingerprints and diagnostic ratios of target compounds from that of spill sample 1460. This was caused most likely by percentages of diesel to lube oil in these two samples different from that in spill sample 1460.     

A survey on the temporal and spatial distribution of perchlorate in the Potomac River

Samples of river water and treated drinking water were obtained from eight sites along the Potomac River between western Maryland and Washington DC. Samples were collected each month from October 2007 to September 2008 and analyzed for perchlorate by ion chromatography/mass spectrometry. Data on anions were also collected for seven of the twelve months. Data were analyzed to identify spatial and temporal patterns for the occurrence of perchlorate in the Potomac. Over the year of sampling, the largest monthly increase occurred from June to July, with levels then decreasing from July to September. Samples from the period between December and May had lower perchlorate concentrations, relative to the remainder of the study year. Spatially, higher levels of perchlorate were found at sites located in west-central Maryland, the eastern panhandle of West Virginia, and central northern Virginia, with levels decreasing slightly as the Potomac approaches Washington DC. Within the sampling boundaries, river (untreated) water perchlorate concentrations ranged from 0.03 μg L(-1) to 7.63 μg L(-1), averaged 0.67 ± 0.97 μg L(-1) over the year-long period and had a median value of 0.37 μg L(-1). There was no evidence that any of the existing drinking water treatment technologies at the sampling sites were effective in removing perchlorate. There were no correlations found between the presence of perchlorate and any of the anions or water quality parameters examined in the source water with the exception of a weak positive correlation with water temperature. Results from the summer (June-August) and fall (September-November) months sampled in this study were generally higher than from the winter and spring months (December-May). All but one of the locations had annual average perchlorate levels below 1 μg L(-1); however, 7 of the 8 sites sampled had river water perchlorate detections over 1 μg L(-1) and 5 of the 8 sites had treated water detections over this level.     

Effectiveness of amendments on re-acidification and heavy metal immobilization in an extremely acidic mine soil

Previous studies have shown that the application of soil amendments is efficient in reducing acidity and heavy metal bioavailability in mine soils. However, it remains a challenge for environmentalists to predict accurately and control economically the re-acidification in re-vegetated mine soils. In this study, net acid generation (NAG) test and bioassay technique were employed to assess the effectiveness of the amendments [including lime, N-P-K (nitrogen, phosphorous and potassium) fertilizer, phosphate and river sediment] on re-acidification and heavy metal immobilization in an extremely acid (pH < 3) mine soil. Our results suggested that NAG test was a rapid and accurate approach to assess the effectiveness of the amendments on re-acidification potential of the mine soil. Interestingly, it was found that phosphate and river sediment played quite specific roles in preventing the re-acidification in the mine soil. In addition, the results also indicated that the addition of 25 t ha(-1) lime combined with river sediment (30%) might be an economical method to successfully control the acidification and re-acidification in the extremely acid mine soil, allowing the re-establishment of the plants. Collectively, our results implied that the combined use of NAG test and bioassay assessment was effective in evaluating a reclamation strategy for extremely acidic mine soils.     

Occurrence and distribution of organophosphorus flame retardants and plasticizers in anthropogenically affected groundwater

Occurrence and distribution of chlorinated and non-chlorinated organophosphates in 72 groundwater samples from Germany under different recharge/infiltration conditions were investigated. Tris(2-chloro-1-methylethyl) phosphate (TCPP) and tris(2-chloroethyl) phosphate (TCEP) were the most frequently detected organophosphates in groundwater samples. Highest individual organophosphate concentrations (>0.1 μg L(-1)) were determined in groundwater polluted by infiltrating leachate and groundwater recharged via riverbank filtration of organophosphate-loaded recipients. In samples from springs and deep groundwater monitoring wells that are not affected by surface waters, organophosphate concentrations were mostly below the limit of detection. The occurrence (3-9 ng L(-1)) of TCPP and TCEP in samples from aquifers with groundwater ages between 20 and 45 years indicates the persistence of both compounds within the aquifer. At urban sites organophosphate-loaded precipitation, surface runoff, and leakage of wastewater influenced groundwater quality. For rural sites, where groundwater recharge is only influenced by precipitation, organophosphates were very rarely detectable in groundwater.     

A uniform fish consumption advisory protocol for the Ohio River

ORSANCO and the six Ohio River main stem states have been working to align states' fish consumption advisories (FCAs) to enhance the value of advice issued to the public. To achieve this goal, ORSANCO worked closely with a panel consisting of state and USEPA representatives. The result of this effort is the Ohio River Fish Consumption Advisory Protocol (ORFCAP). The ORFCAP represents a single set of variables agreed upon by the panel that allows for a standardized protocol to create advisory thresholds to which states can defer to issue consumption advice for the Ohio River. The ORFCAP identifies ORSANCO as a clearinghouse for data which will be distributed to the panel for decision making. Other components include identifying primary contaminants of concern (PCBs and mercury) and dividing the river into four reporting units. The protocol was developed to issue FCAs for the protection of sensitive populations using five advisory groupings for PCBs and four for mercury. Specific variables used in the calculation of advisory thresholds such as health protection values, cooking reductions, average meal sizes, etc., were selected by the panel. Lastly, the protocol calls for FCA decisions to be based on analysis of the most recent 10?years of data for each species in each reporting unit to determine size class needs and advisory groupings. Upon pending implementation of the protocol by the main stem states, these decisions will be made annually through a series of discussions involving ORSANCO, the panel, and other appropriate state personnel.