Soil organic matter carbon chemistry signatures, hydrophobicity and humification index following land use change in temperate peat soils.

Peatlands play a critical role in the global carbon cycle, storing large amounts of carbon because of a net imbalance between primary production and the microbial decomposition of the organic matter. Nevertheless, peatlands have historically been drained for energy sources (e.g. peat briquettes), forestry, or agriculture - practices that could affect the quality of the soil organic matter (SOM) composition, hydrophobicity and humification index. This study compared the effect of land use change on the quality and composition of peatland organic material in Co-Offaly, Ireland. Specifically, drained and grazing peat (grassland), drained and forest plantation peat (forest plantation), drained and industrial cutaway peat (cutaway bog) and an undrained actively accumulating bog (as a reference for natural peatland) were studied. Fourier-transform infrared spectroscopy (FTIR) was used to examine the organic matter quality, specifically the degree of decomposition (DDI), carbon chemistry signatures, hydrophobicity and humification index. The ratio of hydrophobic to hydrophilic group intensities was calculated as the SOM hydrophobicity. In general, there is greater variance in the carbon chemistry signature, such as aliphatic methyl and methylene, C=O stretching of amide groups, aromatic C=C, strong H-bond C=O of conjugated ketones and O-H deformation and C- O stretching of phenolics and secondary alcohols of the peat samples from industrial cutaway bog samples than in the grassland and forest plantation samples. The hydrophobicity and the aromaticity of the soil organic matter (SOM) are significantly impacted by land use changes, with a trend of order active bog > forest plantation > industrial cutaway bog > grassland. A comparison of the degree of decomposition index of the peat from active bog showed a more advanced state of peat degradation in grassland and industrial cutaway bog and, to a lesser extent, in forest plantation.

Assessment of the disinfection capacity and eco-toxicological impact of atmospheric cold plasma for treatment of food industry effluents.

Generation of wastewater is one of the main environmental sustainability issues across food sector industries. The constituents of food process effluents are often complex and require high energy and processing for regulatory compliance. Wastewater streams are the subject of microbiological and chemical criteria, and can have a significant eco-toxicological impact on the aquatic life. Thus, innovative treatment approaches are required to mitigate environmental impact in an energy efficient manner. Here, dielectric barrier discharge atmospheric cold plasma (ACP) was evaluated for control of key microbial indicators encountered in food industry effluent. This study also investigated the eco-toxicological impact of cold plasma treatment of the effluents using a range of aquatic bioassays. Continuous ACP treatment was applied to synthetic dairy and meat effluents. Microbial inactivation showed treatment time dependence with significant reduction in microbial populations within 120 s, and to undetectable levels after 300 s. Post treatment retention time emerged as critical control parameter which promoted ACP bacterial inactivation efficiency. Moreover, ACP treatment for 20 min achieved significant reduction (≥2 Log10) in Bacillus megaterium endospores in wastewater effluent. Acute aquatic toxicity was assessed using two fish cell lines (PLHC-1 and RTG-2) and a crustacean model (Daphnia magna). Untreated effluents were toxic to the aquatic models, however, plasma treatment limited the toxic effects. Differing sensitivities were observed to ACP treated effluents across the different test bio-assays in the following order: PLHC-1 > RTG-2 ≥ D. magna; with greater sensitivity retained to plasma treated meat effluent than dairy effluent. The toxic effects were dependent on concentration and treatment time of the ACP treated effluent; with 30% cytotoxicity in D. magna and fish cells observed after 24 h of exposure to ACP treated effluent for concentrations up to 5%. The findings suggest the need to employ wider variety of aquatic organisms for better understanding and complete toxicity evaluation of long-term effects. The study demonstrates the potential to tailor ACP system parameters to control pertinent microbial targets (mono/poly-microbial, vegetative or spore form) found in complex and nutritious wastewater effluents whilst maintaining a safe eco-toxicity profile for aquatic species.

Integration of biological effects, fish histopathology and contaminant measurements for the assessment of fish health: A pilot application in Irish marine waters.

This study investigates the use of a weight of evidence (WOE) approach to evaluate fish health status and biological effects (BEs) of contaminants for assessment of ecosystem health and discusses its potential application in support of the Marine Strategy Framework Directive (MSFD). External fish disease, liver histopathology and several BEs of contaminant exposure including 7-ethoxy resorufin O-de-ethylase (EROD), acetylcholinesterase (AChE), bile metabolites, vitellogenin (VTG) and alkali labile phosphates (ALP) were measured in two flatfish species from four locations in Ireland. Contaminant levels in fish were generally low with PCBs in fish liver below OSPAR environmental assessment criteria (EAC). There were consistencies with low PCB levels, EROD and PAH bile metabolite levels detected in fish. Dab from Cork, Dublin and Shannon had the highest relative prevalence of liver lesions associated with the carcinogenic pathway. An integrated biomarker response (IBR) showed promise to be useful for evaluation of environmental risk, although more contaminant parameters in liver are required for a full assessment with the present study.

Integrated indicator framework and methodology for monitoring and assessment of hazardous substances and their effects in the marine environment.

Many maritime countries in Europe have implemented marine environmental monitoring programmes which include the measurement of chemical contaminants and related biological effects. How best to integrate data obtained in these two types of monitoring into meaningful assessments has been the subject of recent efforts by the International Council for Exploration of the Sea (ICES) Expert Groups. Work within these groups has concentrated on defining a core set of chemical and biological endpoints that can be used across maritime areas, defining confounding factors, supporting parameters and protocols for measurement. The framework comprised markers for concentrations of, exposure to and effects from, contaminants. Most importantly, assessment criteria for biological effect measurements have been set and the framework suggests how these measurements can be used in an integrated manner alongside contaminant measurements in biota, sediments and potentially water. Output from this process resulted in OSPAR Commission (www.ospar.org) guidelines that were adopted in 2012 on a trial basis for a period of 3 years. The developed assessment framework can furthermore provide a suitable approach for the assessment of Good Environmental Status (GES) for Descriptor 8 of the European Union (EU) Marine Strategy Framework Directive (MSFD).

Application of a weight of evidence approach utilising biological effects, histopathology and contaminant levels to assess the health and pollution status of Irish blue mussels (Mytilus edulis).

A weight of evidence (WOE) approach, integrating biological effects, mussel histopathology and tissue contaminant levels is proposed to evaluate mussel health and pollution status. Contaminant levels, histopathology and several biological effects (BEs) including Lysosomal membrane stability (LMS), acetylcholinesterase (AChe), metallothionein proteins (MT) and alkali labile phosphate (ALP), in Mytilus edulis are presented, improving the current knowledge base for these data. Potential links between histopathology, BEs and contaminants and ranking of sites are investigated with an integrated response (IR) indexing technique. Histopathological condition indices (Ih) in mussel digestive gland are used to calculate health indices. A spatial and temporal assessment is conducted at Irish coastal locations. Linear mixed effects modelling revealed effects of confounding factors such as reproductive condition on NRRT (gonad stage (p < 0.001)). Higher prevalence of inflammation, brown cells and epithelial thinning of the digestive gland was evident at Dublin and Wexford and this linked well with the Ih. Levels of contaminants were generally found to be low with few exceptions as were BE responses. Using the IR approach, Dublin was ranked as being most impacted while Shannon ranked the least impacted, this being consistent with the BE ranking.

In vitro screening of organotin compounds and sediment extracts for cytotoxicity to fish cells.

The present study reports an in vitro screening method for contaminants in sediment samples utilizing an RTG-2 cell line. This technique integrates cytotoxicity testing with analytical chemistry with the aim of achieving a toxicity evaluation of the sediment sample. The toxic effect of individual organotin (OT) compounds and their presence in the sediment sample is the focus of the present study; however, other contaminants are also discussed. The following OT compounds: tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT), triphenyltin (TPT), diphenyltin (DPT), and a sediment solvent extract are exposed to the RTG-2 fish cell line. Both the alamar blue (AB) and neutral red (NR) assays are used to assess cytotoxicity after 24-h and 96-h exposure. Methodology for preparation of a sediment solvent extract suitable for biological testing and analytical determination is also described. With the RTG-2 cells, the AB and NR assays had comparable sensitivity for each individual OT compound exposure after 24 h, with TPT being the most toxic compound tested. The individual OT compound concentrations required to induce a 50% toxic effect on the cells (369 ng ml⁻¹ TBT, 1,905 ng ml⁻¹ DBT) did not equate to the concentrations of these contaminants present in the sediment extract that induced a 50% effect on the cells (294 ng ml⁻¹ TBT, 109 ng ml⁻¹ DBT). The solvent extract therefore exhibited a greater toxicity, and this suggests that the toxic effects observed were not due to OT compounds alone. The presence of other contaminants in the solvent extract is confirmed with chemical analysis, warranting further toxicity testing of contaminant mixtures and exposure to the cell line to further elucidate a complete toxicity evaluation.

Use of caged Nucella lapillus and Crassostrea gigas to monitor tributyltin-induced bioeffects in Irish coastal waters.

Caging studies have been previously reported to be useful for providing valuable information on biological effects of mollusks over short periods of time where resident species are absent. The degree of imposex in caged dog whelk (Nucella lapillus), was measured using the vas deferens sequence index (VSDI) and the Relative Penis Size Index (RPSI) and the extent of shell thickening in caged Pacific oyster (Crassostrea gigas) was investigated at t = 0 and t = 18 weeks. Nucella lapillus, when provided with mussels as a food source at the control site at Omey Island on the west Irish coast, did not demonstrate imposex features, whereas those transplanted to port areas did. Dunmore East exhibited the highest level of imposex (3.25 VDSI and 2.37 RPSI). Shell thickening was evident in C. gigas transplanted to Dunmore East, with low effects evident at the control location, Omey Island, and Dublin Bay at t = 18 weeks. Dry weight whole-body concentrations of organotins were most elevated in all species held at Dunmore East compared with other locations. Greatest delta15N and delta13C enrichment was observed within the tissues of the predatory N. lapillus in all three test sites. Increased assimilation in the Dublin Bay oysters might have been influenced by the presence of more nutrients at this location. Surficial sediment organotin levels were most elevated in the Dunmore East <2-mm fraction (22,707 microg tributyltin/kg dry weight), whereas low organotin levels were determined from Dublin and Omey Island sediments. The valuable application of cost-effective caging techniques to deliver integrated biological effects and chemical measurements in the absence of resident gastropod populations in potential organotin/tributyltin hotspot locations is discussed.

Bioassay-directed fractionation of marine sediment solvent extracts from the east coast of Ireland.

Crude solvent extracts were prepared from three sediment sites in Ireland namely Bull Lagoon, Dunmore East and Dublin Port. These were assayed with Tisbe battagliai and the Microtox system. The extracts were chemically characterised using a variety of analytical techniques for a suite of organic contaminants. Metals and organic contaminant concentration data are reported for the three sites. On the basis of determined toxicity and chemical analysis of these crude extracts, a further bioassay-directed fractionation (BDF) employing the Dunmore East crude organic extract was conducted in addition to chemical analysis. For the crude extracts, T. battagliai and Microtox system demonstrated an order of decreasing toxicity for each of the three sites to be Dublin Port>Dunmore East>Bull Lagoon. Microtox system EC10 values after 30min exposure were 1.08%, 11.6% and 26.9% solvent extract for these sites, respectively. Fractionation of the Dunmore East extract revealed that fraction 1 was the most toxic fraction to both the T. battagliai and the Microtox system demonstrating EC50's after 48 h and 30 min of 44.7% and 16.8% solvent extract for the T. battagliai and Microtox assays, respectively. T. battagliai however did show increased sensitivity to fraction 3 when comparing EC10 values and demonstrated an EC10 value of 17.8% solvent extract after 48h. Fraction 1 was shown to contain the highest quantity of the butyltins, in particular TBT in relation to fractions 2 and 3. A useful BDF technique was developed and employed in this study.

A test battery approach to the ecotoxicological evaluation of cadmium and copper employing a battery of marine bioassays.

Heavy metals are ubiquitous contaminants of the marine environment and can accumulate and persist in sediments. The toxicity of metal contaminants in sediments to organisms is dependent on the bioavailability of the metals in both the water and sediment phases and the sensitivity of the organism to the metal exposure. This study investigated the effects of two metal contaminants of concern (CdCl(2) and CuCl(2)) on a battery of marine bioassays employed for sediment assessment. Cadmium, a known carcinogen and widespread marine pollutant, was found to be the least toxic of the two assayed metals in all in vivo tests. However, CdCl(2) was found to be more toxic to the fish cell lines PLHC-1 and RTG-2 than CuCl(2). Tisbe battagliai was the most sensitive species to both metals and the Microtox and cell lines were the least sensitive (cadmium was found to be three orders of magnitude less toxic to Vibrio fischeri than to T. battagliai). The sensitivity of Tetraselmis suecica to the two metals varied greatly. Marine microalgae are among the organisms that can tolerate higher levels of cadmium. This hypothesis is demonstrated in this study where it was not possible to derive an EC(50) value for CdCl(2) and the marine prasinophyte, T. suecica. Conversely, CuCl(2) was observed to be highly toxic to the marine alga, EC(50) of 1.19 mg l(-1). The genotoxic effect of Cu on the marine phytoplankton was evaluated using the Comet assay. Copper concentrations ranging from 0.25 to 2.50 mg l(-1) were used to evaluate the effects. DNA damage was measured as percent number of comets and normal cells. There was no significant DNA damage observed at any concentration of CuCl(2) tested and no correlation with growth inhibition and genetic damage was found.

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.

An integrated approach to the toxicity assessment of Irish marine sediments: validation of established marine bioassays for the monitoring of Irish marine sediments.

This paper describes the ecotoxicological evaluation of marine sediments from three sites around Ireland representative of a range of contaminant burdens. A comprehensive assessment of potential sediment toxicity requires the consideration of multiple exposure phases. In addition to the evaluation of multi-exposure phases the use of a battery of multi-trophic test species has been advocated by a number of researchers as testing of single or few organisms may not detect toxicants with a specific mode of action. The Microtox solid phase test (SPT) and the 10-d acute amphipod test with Corophium volutator were used to assess whole sediment toxicity. Porewater and elutriates were assessed with the Microtox acute test, the marine prasinophyte Tetraselmis suecica, and the marine copepod Tisbe battagliai. Solvent extracts were assayed with the Microtox and T. battagliai acute tests. Alexandra Basin was identified as the most toxic site according to all tests, except the Microtox SPT which identified the Dunmore East site as being more toxic. However, it was not possible to correlate the observed ecotoxicological effects with a specific and/or class of contaminants based on sediment chemistry alone. Therefore porewaters found to elicit significant toxicity (Dunmore East and Alexandra Basin) with the test battery were selected for further TIE assessment with T. battalgiai and the Microtox system. 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.

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.