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.     

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.     

Silver speciation in liver of marine mammals by synchrotron X-ray absorption fine structure and X-ray fluorescence spectroscopies

The chemical form of Ag in the livers of five species of marine mammals was examined using X-ray absorption fine structure (XAFS) and X-ray fluorescence (XRF) spectroscopies. The XAFS analysis suggested that Ag(2)Se was present in the livers of the Franciscana dolphin (Pontoporia blainvillei), Dall's porpoise (Phocoenoides dalli), and Baird's beaked whale (Berardius bairdii), whereas Ag(2)S was present in the livers of the striped dolphin (Stenella coeruleoalba) and pygmy killer whale (Feresa attenuata). XRF spectroscopy results revealed that the distribution patterns of Ag and Se in a thin section of the liver of the Franciscana dolphin were the same; this also implied that Ag was associated with Se in the liver. Thus, the interaction of Ag with Se or S may offer significant protection against the toxicity of Ag in marine mammals. The formation of either Ag(2)Se or Ag(2)S might depend on the Hg levels in the liver. Ag(2)Se was observed in liver samples with relatively high Ag/Hg ratio, whereas liver samples with low Ag/Hg ratio contained Ag(2)S.     

Design and laboratory testing of a new flow-through directional passive air sampler for ambient particulate matter

A new type of directional passive air sampler (DPAS) is described for collecting particulate matter (PM) in ambient air. The prototype sampler has a non-rotating circular sampling tray that is divided into covered angular channels, whose ends are open to winds from sectors covering the surrounding 360°. Wind-blown PM from different directions enters relevant wind-facing channels, and is retained there in collecting pools containing various sampling media. Information on source direction and type can be obtained by examining the distribution of PM between channels. Wind tunnel tests show that external wind velocities are at least halved over an extended area of the collecting pools, encouraging PM to settle from the air stream. Internal and external wind velocities are well-correlated over an external velocity range of 2.0-10.0 m s?1, which suggests it may be possible to relate collected amounts of PM simply to ambient concentrations and wind velocities. Measurements of internal wind velocities in different channels show that velocities decrease from the upwind channel round to the downwind channel, so that the sampler effectively resolves wind directions. Computational fluid dynamics (CFD) analyses were performed on a computer-generated model of the sampler for a range of external wind velocities; the results of these analyses were consistent with those from the wind tunnel. Further wind tunnel tests were undertaken using different artificial particulates in order to assess the collection performance of the sampler in practice. These tests confirmed that the sampler can resolve the directions of sources, by collecting particulates preferentially in source-facing channels.     

Changing patterns of organochlorine pesticide residues in raw bovine milk from Haryana, India

Bovine milk samples were collected and analyzed during 1992 and 1998 from rural areas of 14 different districts of Haryana state for the presence of HCH and DDT residues. The study revealed that the mean residues of ΣHCH in raw bovine milk have declined by 67.5% while mean levels of ΣDDT have decreased by 92.8% during six years gap. The obtained results reveal that during 1992 p,p'-DDT was the main component followed by p,p'-DDD, α-HCH and β-HCH while in 1998, p,p'-DDE and β-HCH followed by p,p'-DDT were relatively more as compared to other isomers and metabolites of these pesticides.     

Hydrologic disturbance reduces biological integrity in urban streams

The impact of urbanization on stream ecosystems is linked by land cover changes to the alteration of the natural hydrology and subsequent physical disruption of stream biota and habitat. Seasonal floods are part of the natural disturbance regime of many streams, but urbanization increases their frequency and magnitude. This study evaluated the impact of hydrologic disturbance on fish and aquatic macroinvertebrates in 81 (56 urban/25 reference) Ohio streams. Hydrologic variables included annual and monthly 24-h rainfall maxima and computed annual peak discharge, with computation supported by GIS-based drainage area delineation and land cover characterization. Ohio biological criteria for fish and macroinvertebrates measured during the late spring and summer were negatively impacted by annual peak discharge in urban streams as compared to reference streams. Results support the application of stormwater best management practices as part of stream restoration efforts to mitigate urbanization impacts to fish and macroinvertebrates.     

Arsenic-safe alternate aquifers and their hydraulic characteristics in contaminated areas of Middle Ganga Plain, Eastern India

Arsenic groundwater contamination exceeding 0.05 mg/l affecting the Newer Alluvial tracts of Patna and Bhojpur, the two worst affected districts located in the Middle Ganga Plain in the Bihar state, has been studied The area is underlain by two-tier Quaternary aquifer systems within a depth of 300 m below ground level, separated by a 15?C32-m-thick clay/sandy clay aquitard. The upper part (<50 m depth) of the shallow aquifer system is arsenic-contaminated. The deeper aquifer system (lying below 120?C130 m depth) exhibits low arsenic load (max 0.0035 mg/l), having hydraulic conductivity between 64.88 and 82.04 m/day. Groundwater in the deeper aquifer occurs under semi-confined to confined condition due to poor hydraulic conductivity of the middle clay (4.7 × 10^???2???7.2 × 10^???3 m/day). Hydraulic head of the deeper aquifer remains close to the surface than the shallow aquifer. The two aquifer systems in the Newer Alluvium are replaced by a thick single aquifer system in the adjoining Older Alluvium, within a depth of 330 m below ground. In the arsenic-contaminated area, deeper aquifer is protected by a middle clay, which may be developed for community drinking water supply by deep tube wells having a yield capacity of 150 m³/h.     

Occurrence of PCBs in raw and finished drinking water at seven public water systems along the Hudson River

Polychlorinated biphenyls (PCBs) were measured in raw and finished drinking water at seven Public Water Systems (PWSs) along the Hudson River as part of a baseline monitoring program prior to the extensive sediment dredging of the Upper Hudson River. Water samples were either analyzed using an Aroclor method (based on USEPA Method 508) or a congener method (Modified Green Bay Mass Balance Method). Using the congener-based method, raw water concentrations ranged from <9.3 to 164.3 ng/L and finished water concentrations ranged from <9.3 to 186.6 ng/L. Using the Aroclor method, finished water concentrations ranged from <5.0 to 200.9 ng/L. Most finished water samples above 73.0 ng/L were from a PWS with wells drilled near the river. Excluding the well data, total PCB concentrations in raw water at systems in the Upper River were similar to concentrations at systems in the Lower River, though the congener patterns differed. Paired comparison of total PCB concentrations using the two analytical methods showed good agreement, although raw water showed a different relationship than finished water.