Issues in monitoring hazardous chemicals in stormwater runoff/discharges from superfund and other hazardous chemical sites

Deficiencies in design and execution render stormwater‐runoff monitoring programs for many hazardous chemical sites inadequate for assessing the potential environmental quality and public health impacts of chemicals in the runoff. Two pervasive problems are the use of analytical methods that are inadequate for measuring certain hazardous chemicals at potentially hazardous concentrations, and the application of “criteria/standards” that are inappropriate for evaluating the environmental/public health impacts of chemicals. These concerns are most notable for carcinogens and chemicals that bioaccumulate in edible aquatic organisms, including arsenic, chromium, beryllium, mercury, dioxins, organochlorine pesticides (such as DDT), and polychlorinated biphenyls; unrecognized pollutants; and nanomaterials. In order to appropriately evaluate whether the runoff/discharge from a hazardous chemical site is a threat to human health, the analytical methods must be sufficiently sensitive in critical concentration ranges; sampling regimens need to be sufficiently rigorous to provide reliable characterization of the content of the runoff, receiving water, and, for bioaccumulatable chemicals, levels in edible organisms in receiving water. Proper sampling and analysis will then provide data to enable the appropriate criteria/standards to be applied. © 2010 Wiley Periodicals, Inc.     

Greenhouse gas emissions from two soils receiving nitrogen fertilizer and swine manure slurry

The interactive effects of soil texture and type of N fertility (i.e., manure vs. commercial N fertilizer) on N(2)O and CH(4) emissions have not been well established. This study was conducted to assess the impact of soil type and N fertility on greenhouse gas fluxes (N(2)O, CH(4), and CO(2)) from the soil surface. The soils used were a sandy loam (789 g kg(-1) sand and 138 g kg(-1) clay) and a clay soil (216 g kg(-1) sand, and 415 g kg(-1) clay). Chamber experiments were conducted using plastic buckets as the experimental units. The treatments applied to each soil type were: (i) control (no added N), (ii) urea-ammonium nitrate (UAN), and (iii) liquid swine manure slurry. Greenhouse gas fluxes were measured over 8 weeks. Within the UAN and swine manure treatments both N(2)O and CH(4) emissions were greater in the sandy loam than in the clay soil. In the sandy loam soil N(2)O emissions were significantly different among all N treatments, but in the clay soil only the manure treatment had significantly higher N(2)O emissions. It is thought that the major differences between the two soils controlling both N(2)O and CH(4) emissions were cation exchange capacity (CEC) and percent water-filled pore space (%WFPS). We speculate that the higher CEC in the clay soil reduced N availability through increased adsorption of NH(4)(+) compared to the sandy loam soil. In addition the higher average %WFPS in the sandy loam may have favored higher denitrification and CH(4) production than in the clay soil.     

A metabolomics based approach to assessing the toxicity of the polyaromatic hydrocarbon pyrene to the earthworm Lumbricus rubellus

The biochemical response of the earthworm Lumbricus rubellus to pyrene exposure was assessed using 1H nuclear magnetic resonance (NMR) spectroscopy, gas chromatography mass spectrometry (GC-MS) and pattern recognition techniques. Both analytical methods enabled the establishment of reproducible metabolic profiles. NMR analysis identified a total of 32 metabolites while GC-MS identified 51. The results demonstrate that not only is pyrene toxic to L. rubellus, but that alterations in its normal metabolic profile could be observed even when individuals were exposed to concentrations of 40mg kg(-1): a pollution level that is both below the concentration previously found to significantly reduce reproduction and within the range of polycyclic aromatic hydrocarbons (PAHs) found on some contaminated sites. Pyrene was found to cause a dose dependant decrease in lactate and the concentrations of the saturated fatty acids tetradecanoic, hexadecanoic and octadecanoic acid and an increase in production of the amino acids alanine, leucine, valine, isoleucine, lysine, tyrosine and methionine. It is proposed that this indicates impaired glucose metabolism, with an associated increase in fatty acid metabolism and changes in TCA cycle intermediates. This study demonstrates the versatility of metabolomics as a tool to monitor toxicity in the environment as opposed to utilising model species studied in a laboratory setting. Since it is a non-carcinogenic PAH, we propose that the metabolic changes observed in worms may reflect the non-specific toxic effects of pyrene as a typical, non-polar organic compound.     

Understanding levels and trends of BDE-47 in the UK and North America: an assessment of principal reservoirs and source inputs

Despite increasing interest in the occurrence of Polybrominated diphenyl ethers (PBDEs) in the environment, there has been only limited effort expended to identify principal source input reservoirs and pathways into the environment. Taking a single congener BDE-47, an important component of the penta commercial product, we have estimated principal contemporary reservoirs and emissions in two regions with very different historical use patterns. In North America, production and use of the penta-product has been rising steadily for the last 20 years, whilst in the UK, use has been restricted over the last 10 years, and most recently, there has been an EU ban on use. Mass balance models have been applied using our contemporary emission estimates to predict environmental levels. Results highlight that contemporary emissions to air can account for contemporary air concentrations but cannot account for measured concentrations in principal reservoirs such as soils and sediments. Future efforts are needed to improve our knowledge of the stocks of PBDEs in use, and emission factors from those stocks, to better understand/predict past and likely future trends.     

Short and medium chain length chlorinated paraffins in UK human milk fat

Chlorinated paraffins (also called polychlorinated n-alkanes -- PCAs) are a class of industrial chemicals comprising chlorinated straight chain hydrocarbons. They have a wide range of applications and are now found in a range of environmental compartments. We analysed a total of 25 human milk-fat samples, donated by 18 individuals from the urban London and more rural Lancaster areas in the UK, for short chain PCAs (C(10)-C(13) sPCAs) and medium chain PCAs (C(14)-C(17) mPCAs), using gas chromatography-ECNI high-resolution mass spectrometry. Our study confirms that trace quantities of PCAs can reach human milk-fat. sPCAs were detected in all but four samples, while mPCAs were detected in all samples. The median sPCA concentration was 180 ng/g fat (range of 49 to 820 ng/g fat -- detected values only) and the median mPCA concentration was 21 ng/g fat (range of 6.2 to 320 ng/g fat). No differences were noted in ranges of observed values for either sPCAs or mPCAs between samples from London and Lancaster. Most samples also exhibited similar patterns of sPCAs and mPCAs. One sample exhibited a different pattern for sPCAs and mPCAs, an observation that may be related to differences in exposure or biological factors for this individual.     

Improving public health and environmental protection resulting from Superfund site investigation/remediation

A discussion of some of the deficiencies of Superfund and hazardous chemical site investigation and remediation is presented. Of concern is the adequacy of defining the constituents of concern; stormwater‐runoff monitoring; evaluating excessive bioaccumulation of hazardous chemicals in edible organisms; the extent and degree of groundwater pollution; modeling of pollutant transport in the vadose zone; translocation of subsurface pollutants to surface via plant roots, leaves, and flowers; protection of groundwater quality for nonpriority pollutants that impact aesthetic quality; and deficiencies in the quality of site data reports. Examples of these types of problems are discussed with suggestions on the approach that should be followed to improve the quality of site investigation and remediation. © 2004 Wiley Periodicals, Inc.     

Macroinvertebrate assemblages of surface mine wetlands of Southwest Virginia,USA

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Perfluorinated compounds in water, sediment, soil and biota from estuarine and coastal areas of Korea

Soil, sediment, water, and biota collected from the western coast of Korea were analyzed to determine occurrence and sources of perfluorinated compounds (PFCs). PFCs were significantly concentrations of PFCs were measured in some water and biological samples, while concentrations of PFCs in soils and sediments were relatively low. The most widely detected compound was found to be perfluorooctanesulfonate (PFOS), with a maximum concentration in water of 450 ng/L and in fish of 612 ng/g, dw. PFOS concentrations in water and biota were both less than those thought to cause toxicity. However, in both cases concentrations were within a factor of 10 of the toxicity threshold concentration. Concentrations of PFCs were significantly greater downstream than those upstream on the same river, suggesting point sources. Overall, the detection of PFCs at relatively great concentrations in various environmental matrixes from this region of Korea suggests that further studies characterizing PFCs and their potential risk to both humans and wildlife are needed.     

Measurement of total site mercury emissions from a chlor-alkali plant using ultraviolet differential optical absorption spectroscopy and cell room roof-vent monitoring

This technical note describes a United States Environmental Protection Agency (U.S. EPA) measurement project to determine elemental mercury (Hg⁰) emissions from a mercury cell chlor-alkali (MCCA) facility in the southeastern U.S. during a 53-day monitoring campaign in the fall of 2006. The optical remote sensing (ORS) area source measurement method EPA OTM 10 was used to provide Hg⁰ flux data for the site. These results are reported and compared with cell room roof-vent monitoring data acquired by the facility for similar time periods. The 24-h extrapolated mercury emission rate estimates determined by the two monitoring approaches are shown to be similar with overall averages in the 400 g day^?1 range with maximum values around 1200 g day^?1. Results from the OTM 10 measurements, which include both cell room emissions and potential fugitive sources outside the cell room, are shown to be approximately 10% higher than cell room monitoring results indicating that fugitive emissions from outside the cell room produce a small but measurable effect for this site.