An integrated approach to the toxicity assessment of Irish marine sediments: application of porewater Toxicity Identification Evaluation (TIE) to Irish marine sediments

An integrated approach to the ecotoxicological assessment of Irish marine sediments was carried out between 2004 and 2007. Phase I Toxicity Identification Evaluation (TIE) of sediment porewaters from two sites on the east coast of Ireland were conducted. Initial Tier I screening of three Irish sites identified the need for TIE after significant toxicity was observed with Tisbe battagliai and the Microtox assay at two of the assayed sites (Alexandra Basin and Dunmore East). Porewaters classified as toxic were characterised using four manipulations, ethylenediaminetetraacetic acid (EDTA) chelation, sodium thiosulphate addition, C(18) Solid Phase Extraction (SPE) and Cation Exchange (CE) SPE. Prior to initial testing, and TIE manipulations, all porewater samples were frozen at -20 degrees C for several months until required. After initial Tier I testing Alexandra Basin porewater was classified as highly toxic by both assays while Dunmore East porewater only warranted a TIE with T. battagliai. Results of TIE manipulations for Alexandra Basin porewater and the Microtox Basic test were inconclusive. The toxicity of the porewater in this assay was significantly reduced after freezing. Three experimental episodes were conducted with one month between each for the Alexandra Basin porewater. After each month of freezing the baseline toxicity was further reduced in the Microtox assay, therefore it was not possible to draw accurate conclusions on the nature of the active contaminants in the sample. However, toxicity to T. battalgiai did not change after storage of the porewater. The C(18) and CE SPE decreased the toxicity of Alexandra Basin porewater to the copepod indicating that both organic and cationic compounds (e.g. metals) were active in the sample. Dunmore East porewater was assayed with T. battalgiai and again a combination of organic and inorganic compounds were found to be partly responsible for the observed toxicity (C(18), CE SPE and EDTA reduced toxicity). Results from these TIEs provide insight into the complexity of interpreting marine TIE data from porewater studies where mixtures of unknown substances are present.     

Mechanisms of molecular product and persistent radical formation from the pyrolysis of hydroquinone

Hydroquinone is considered to be one of the major, potential molecular precursors for semiquinone-type radicals in the combustion of complex polymeric and oligomeric structures contained in biomass materials. Comprehensive product yield determinations from the high-temperature, gas-phase pyrolysis of hydroquinone in two operational modes (rich and lean hydrogen conditions) are reported at a reaction time of 2.0s over a temperature range of 250-1000 degrees C. Below 500 degrees C, p-benzoquinone is the dominant product, while at temperatures above 650 degrees C other products including phenol, benzene, styrene, indene, naphthalene, biphenylene, phenylethyne, dibenzofuran and dibenzo-p-dioxin are formed. Hydrogen-rich conditions initially inhibit hydroquinone decomposition (below 500 degrees C) but promote product formation at higher temperatures. The decomposition process apparently proceeds via formation of a resonance stabilized p-semiquinone radical. Detailed mechanisms of formation of stable molecular species as well as stable radicals are proposed.     

A model compound study: the ecotoxicological evaluation of five organic contaminants employing a battery of marine bioassays

This paper describes the ecotoxicological evaluation of five organic contaminants frequently detected in marine sediments (tributyltin, triphenyltin, benzo[a]pyrene, fluoranthene, and PCB 153) using three marine species (Vibrio fischeri, Tetraselmis suecica, and Tisbe battagliai). The sensitivity of each species varied for all compounds. The triorganotins were consistently the most toxic to all species. The applicability of each test system to assess the acute toxicity of environmental contaminants and their use in Toxicity Identification Evaluation (TIE) is discussed. Suitability of the Microtox and T. battagliai tests for employment in TIE studies were further assessed through spiking experiments with tributyltin. Results demonstrated that the most effective treatment to remove organotin toxicity from the sample was the C18 resin. The results of this study have important implications for risk assessment in estuarine and coastal waters in Ireland, where, at present the monitoring of sediment and water quality is predominantly reliant on chemical analysis alone.     

The Validation of a Passive Sampler for Indoor and Outdoor Concentrations of Volatile Organic Compounds

Abstract

Volatile organlcs compounds (VOCs) are ubiquitous in the air we breathe. The use of passive samplers to measure these concentrations can be an effective technique. When exposed for long durations, a passive sampler may be a good tool for investigating chronic exposures to chemicals in the environment. A passive sampler that was designed for occupational exposures can be used as such a tool. Laboratory validation under as many conditions as possible needs to be accomplished so as to characterize the sampler with known parameters. This paper describes the methods and results of an investigation into the validity of using a passive monitor to sample VOCs for a three-week period. Two concentration levels, two relative humidities, and five VOCs were studied. Results indicate that the samplers work best under conditions of high concentration with low relative humidity and low concentration with high relative humidity. For the passive sampler, excluding chloroform, percent deviations from the predicted values varied between ?41 and +22 percent; while the values between the passive and the active samplers varied between ?27 and +24 percent. Benzene, heptane, and perchloroethylene were sampled with equal precision and accuracy.     

Wildfire,climate, and perceptions in Northeast Oregon

Regional Environmental Change - Wildfire poses a rising threat in the western USA, fueled by synergies between historical fire suppression, changing land use, insects and disease, and shifts toward...     

Climate Change and Forest Communities: Prospects for Building Institutional Adaptive Capacity in the Congo Basin Forests

Tropical forests are vulnerable to climate-change representing a risk for indigenous peoples and forest-dependent communities. Mechanisms to conserve the forest, such as REDD+, could assist in the mitigation of climate change, reduce vulnerability, and enable people to adapt. Ninety-eight interviews were conducted in three countries containing the Congo Basin forest, Cameroon, CAR, and DRC, to investigate perceptions of decision-makers within, and responses of the institutions of the state, private sector, and civil society to the challenges of climate change. Results indicate that while decision-makers’ awareness of climate change is high, direct institutional action is at an early stage. Adaptive capacity is currently low, but it could be enhanced with further development of institutional linkages and increased coordination of multilevel responses across all institutions and with local people. It is important to build networks with forest-dependent stakeholders at the local level, who can contribute knowledge that will build overall institutional adaptive capacity.     

5:3 Polyfluorinated acid aerobic biotransformation in activated sludge via novel "one-carbon removal pathways"

The polyfluorinated carboxylic acids 5:3 acid (C₅F₁₁CH₂CH₂CO₂H) and 7:3 acid (C₇F₁₅CH₂CH₂CO₂H) are major products from 6:2 FTOH (C₆F₁₃CH₂CH₂OH) and 8:2 FTOH (C₈F₁₇CH₂CH₂OH) aerobic biotransformation, respectively. The 5:3 and 7:3 acids were dosed into domestic WWTP activated sludge for 90 d to determine their biodegradability. The 7:3 acid aerobic biodegradability was low, only 1.7 mol% conversion to perfluoroheptanoic acid (PFHpA), whereas no transformation was observed previously in soil. In stark contrast, 5:3 acid aerobic biodegradability was enhanced 10 times in activated sludge compared to soil. The 5:3 acid was not activated by acyl CoEnzyme A (CoA) synthetase, a key step required for further α- or ß-oxidation. Instead, 5:3 acid was directly converted to 4:3 acid (C₄F₉CH₂CH₂CO₂H, 14.2 mol%) and 3:3 acid (C₃F₇CH₂CH₂CO₂H, 0.9 mol%) via “one-carbon removal pathways”. The 5:3 acid biotransformation also yielded perfluoropentanoic acid (PFPeA, 5.9 mol%) and perfluorobutanoic acid (PFBA, 0.8 mol%). This is the first report to identify key biotransformation intermediates which demonstrate novel one-carbon removal pathways with sequential removal of CF₂ groups. Identified biotransformation intermediates (10.2 mol% in sum) were 5:3 Uacid, α-OH 5:3 acid, 5:2 acid, and 5:2 Uacid. The 5:2 Uacid and 5:2 acid are novel intermediates identified for the first time which confirm the proposed pathways. In the biodegradation pathways, the genesis of the one carbon removal is CO₂ elimination from α-OH 5:3 acid. These results suggest that there are enzymatic mechanisms available in the environment that can lead to 6:2 FTOH and 5:3 acid mineralization. The dehydrogenation from 5:3 acid to 5:3 Uacid was the rate-limiting enzymatic step for 5:3 acid conversion to 4:3 acid.     

The occurrence of glyphosate, atrazine, and other pesticides in vernal pools and adjacent streams in Washington, DC, Maryland, Iowa, and Wyoming, 2005–2006

Vernal pools are sensitive environments that provide critical habitat for many species, including amphibians. These small water bodies are not always protected by pesticide label requirements for no-spray buffer zones, and the occurrence of pesticides in them is poorly documented. In this study, we investigated the occurrence of glyphosate, its primary degradation product aminomethylphosphonic acid, and additional pesticides in vernal pools and adjacent flowing waters. Most sampling sites were chosen to be in areas where glyphosate was being used either in production agriculture or for nonindigenous plant control. The four site locations were in otherwise protected areas (e.g., in a National Park). When possible, water samples were collected both before and after glyphosate application in 2005 and 2006. Twenty-eight pesticides or pesticide degradation products were detected in the study, and as many as 11 were identified in individual samples. Atrazine was detected most frequently and concentrations exceeded the freshwater aquatic life standard of 1.8 micrograms per liter (microg/l) in samples from Rands Ditch and Browns Ditch in DeSoto National Wildlife Refuge. Glyphosate was measured at the highest concentration (328 microg/l) in a sample from Riley Spring Pond in Rock Creek National Park. This concentration exceeded the freshwater aquatic life standard for glyphosate of 65 microg/l. Aminomethylphosphonic acid, triclopyr, and nicosulfuron also were detected at concentrations greater than 3.0 microg/l.     

Chronic and episodic acidification of Adirondack streams from acid rain in 2003-2005

Limited information is available on streams in the Adirondack region of New York, although streams are more prone to acidification than the more studied Adirondack lakes. A stream assessment was therefore undertaken in the Oswegatchie and Black River drainages; an area of 4585 km(2) in the western part of the Adirondack region. Acidification was evaluated with the newly developed base-cation surplus (BCS) and the conventional acid-neutralizing capacity by Gran titration (ANC(G)). During the survey when stream water was most acidic (March 2004), 105 of 188 streams (56%) were acidified based on the criterion of BCS < 0 microeq L(-1), whereas 29% were acidified based on an ANC(G) value < 0 microeq L(-1). During the survey when stream water was least acidic (August 2003), 15 of 129 streams (12%) were acidified based on the criterion of BCS < 0 microeq L(-1), whereas 5% were acidified based on ANC(G) value < 0 microeq L(-1). The contribution of acidic deposition to stream acidification was greater than that of strongly acidic organic acids in each of the surveys by factors ranging from approximately 2 to 5, but was greatest during spring snowmelt and least during elevated base flow in August. During snowmelt, the percentage attributable to acidic deposition was 81%, whereas during the October 2003 survey, when dissolved organic carbon (DOC) concentrations were highest, this percentage was 66%. The total length of stream reaches estimated to be prone to acidification was 718 km out of a total of 1237 km of stream reaches that were assessed.     

Physical and chemical properties of feedlot pen surfaces located on moderately coarse- and moderately fine-textured soils in southern Alberta

Southern Alberta has the highest density of feedlot cattle in Canada, and there is a concern that leaching of water and contaminants may be greater for feedlots located on coarser-textured than finer-textured soils. Our objective was to determine if infiltration and leaching were greater for a 4-yr-old feedlot located on a moderately coarse-textured (MC) soil compared with two feedlots located on moderately fine-textured (MF) soils (5- and 52-yr-old pens). Various soil physical properties of feedlot pen surfaces were measured, including field-saturated hydraulic conductivity (K(fs)) and near-saturated hydraulic conductivity at -0.9 and -3.9 cm water potential. Selected chemical properties of feedlot soil layers were measured, as well as the chloride content of the soil profile (0-100 cm). Mean K(fs), K(-0.9), and K(-3.9) values were not significantly (P > 0.10) greater at the MC site than the two MF sites, indicating no evidence of greater infiltration on coarser-textured soils. In addition, mean K(fs), K(-0.9), and K(-3.9) values of soils within feedlot pens at all three sites were significantly (P < or = 0.10) reduced by 46 to 78% compared with soil outside the pens. Depth of chloride accumulation was greatest at the 52-yr-old feedlot on MF soil (60-70 cm), followed by 4-yr-old feedlot on MC soil (40-50 cm) and 5-yr-old feedlot on MF soil (30-40 cm). Visual inspection determined that the black interface layer formed within 2 mo of cattle stocking at all three sites.