An investigation of the reactivity and chromatographic separation of some ruthenium bis (2, 2' - bibyridyl) compounds

The complex [Ru(bpy)2(CO)H]PF6 .l/2Acetone was synthesised in 50% yield. The reaction of this complex with a number of aldehydes, ketones and esters in buffered aqueous media and in an acidic acetonitrile environment revealed the reactivity to decrease in this order: Aldehydes > Ketones > Esters A kinetic study into the general acid catalysed reaction of this hydride complex with bgnzal^e^ydj was carried out and a rate coefficient of 1.3 10~ mol 1_| was calculated. An activation energy of 11.5 kJmol was calculated. High Performance Liquid Chromatography (H£LC) was used to demonstrate the conversion of [Ru(bpy)2 (CO)H] to [Ru(bpy)2 (CO)Cl] in acetonitrile by addition of HC1. Reverse phase ion pair chromatography (RP.IPC) and cation exchange chromatography were used for the analysis of ruthenium bis (2,21-bipyridyl), (bpy), complexes using a range of mobile phases with lithium perchlorate, (LiClO^), as an additive. A C18 and a CN column were not suitable for the analysis due to peak distortion problems. A cation exchange, (CX), column provided a useful method for the separation of these compounds. Plots of %acetonitrile, (MeCN), vs. retention time at given LiCl04 concentration suggested a change in the dominant retention mechanism, possibly from cation exchange to RP.IPC with increaing water content in the mobile phase. The presence of split peaks for the dicationic complexes at 80%MeCN : 20%H20 ; 0.1M LiC104 as mobile phase was attributed to competing retention mechanisms. The optimum system for the separation of the compounds examined was 80%MeCN : 20%H„0 ; 0.08M LiC104 at a flow rate of 2.5ml/min. The Photolyses of [Ru(bpy)2L2]2+ [Ru(bpy)2 (L)C1]+ , (L = imidazole / vinylimidazole), in MeCN was studied on an ODS and a CX column using the system developed. The ligand was replaced in these reactions to give [Ru(bpy)2(MeCN)2 ] + for the dicationic compounds and [Ru(bpy)2 (MeCN)Cl] for the monocationic compounds as the major final products. Other unidentified products were present in significant levels. The potential applications of HPLC in the study of ruthenium bis (2,21-bipyridine) complexes were demonstrated by these experiments

A field deployable method for a rapid screening analysis of inorganic arsenic in seaweed

The authors thank the support for getting the seaweed samples from the projects funded under the Department of Agriculture, Food and the Marine’s Competitive research programmes in Ireland. Reference number 14 SF 860. The authors thank Corny Brombach for the graphical abstract.Peer reviewedPublisher PD

Certified Reference Materials for Marine Monitoring

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An Assessment of Dangerous Substances in Water Framework Directive Transitional and Coastal Waters 2007-2009

This report presents an assessment of hazardous substance contamination in Irish transitional and coastal waters. This was carried out in support of the EPA’s assessment of the quality status of surface waters (2007-2009) as required by the Water Framework Directive (Directive 2000/60/EC).Funder: Marine Institut

Biological Effects and Chemical Measurements in Irish Marine Waters

The overall aim of this project was to increase Ireland’s capacity for the generation of integrated monitoring of biological effects and chemical measurement data and for the completion of a pilot scale assessment of the quality of the Irish marine environment at a number of selected locations.Sea Change Strategy with the support of the Marine Institute and the Marine Research Sub Programme of the National Development Plan 2007-2013, and funding from the Environmental Protection Agency (EPA

Catchment approach to passive sampling of Irish waters

The challenges of monitoring our waters for compliance with WFD and the expansion of the list of organic chemicals that are to be added for monitoring, provides impetus for investigation of alternative monitoring approaches such as passive sampling. The work being carried out represents an important collaboration between two research centres (DCU & MI) together with agency (EA UK and Inland Fisheries Ireland) and industry (TelLab) to assess the potential of passive sampling in monitoring priority pollutants in Ireland. The impact of this study may lie in the establishment of a capability to utilise passive sampling in the monitoring programme in Ireland for WFD. This project pilots the use of passive sampling technology (PDMS and POCIS) combined with biota monitoring to assess the presence of priority substances in Irish surface waters. The project focuses in particular on new pollutants earmarked as candidates for the Annex X priority substances list under the EU Water Framework Directive e.g. E2 and EE2, pharmaceuticals, pesticides, PFOS etc. This considers the implications for compliance with current and proposed EQS and investigates the potential for incorporating passive sampling and biota testing in future compliance, investigative and trend monitoring. . Results of water, biota and passive sampling will be presented together for samples collected in the Dublin catchment. A separate study on the occurrence of the pyrethroid pesticide cypermethrin was also conducted. Several sites along the River Liffey, Dublin, were sampled for pharmaceutical as well as other organic pollutants. A POCIS device was deployed at each location and water samples were collected at T-0 and T-4weeks. There are a number of potential point sources of pollution to this catchment with 3 wastewater treatment plants in the area. Pyrethroids have a low toxicity relative to other pesticides (specifically the organochlorines) so have recently been used in place of more toxic pesticides. Cypermethrin has been shown to accumulate in passive sampling devices. This study involved collection of water samples alongside PDMS and SPMD samplers. Cypermethrin was detected in high levels in the water and PDMS samplers. Passive sampling devices can be a useful supporting technique in a ‘toolbox’ for monitoring within the WFD and other environmental programs. From the investigation of work to date it is clear that passive sampling can play an important role in screening of waters for emerging contaminants, especially for hydrophobic subtances where they could be incorporated into a risk based approach to monitoring. Also, passive sampling has demonstrated that it has a role to play in trend monitoring to illustrate where waters are improving in quality over time, thereby offering the WFD monitoring programme a valuable tool. Keywords: passive sampling, surface waters, coastal waters, WFD

Profit-oriented disassembly-line balancing

As product and material recovery has gained importance, disassembly volumes have increased, justifying construction of disassembly lines similar to assembly lines. Recent research on disassembly lines has focused on complete disassembly. Unlike assembly, the current industry practice involves partial disassembly with profit-maximization or cost-minimization objectives. Another difference between assembly and disassembly is that disassembly involves additional precedence relations among tasks due to processing alternatives or physical restrictions. In this study, we define and solve the profit-oriented partial disassembly-line balancing problem. We first characterize different types of precedence relations in disassembly and propose a new representation scheme that encompasses all these types. We then develop the first mixed integer programming formulation for the partial disassembly-line balancing problem, which simultaneously determines (1) the parts whose demand is to be fulfilled to generate revenue, (2) the tasks that will release the selected parts under task and station costs, (3) the number of stations that will be opened, (4) the cycle time, and (5) the balance of the disassembly line, i.e. the feasible assignment of selected tasks to stations such that various types of precedence relations are satisfied. We propose a lower and upper-bounding scheme based on linear programming relaxation of the formulation. Computational results show that our approach provides near optimal solutions for small problems and is capable of solving larger problems with up to 320 disassembly tasks in reasonable time

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

Assuring Seafood Safety: Contaminants and Residues in Irish Seafood 2004-2008

This report provides an overview on the occurrence of environmental contaminants, such as metals and persistent organic pollutants (POPs), and veterinary residues in Irish seafood. Compliance of seafood (shellfish, crustaceans, wild and farmed finfish) with relevant EC Regulatory Limits for contaminants is examined and an overview of conformance of the aquaculture sector with the requirements of the EC Residues Directive (Dir 96/23/EC) is presented for 2004 - 2008. The contribution of seafood to the dietary intake of certain contaminants for the Irish adult seafood consumer is estimated and the risks of contaminant exposure from seafood consumption are considered in the context of the well established health benefits of seafood consumption

CHEMREP 2022-028

On behalf of the Department of Agriculture, Food and Marine (DAFM), the Marine Institute carries out monitoring of chemical residues in finfish for aquaculture sector. This monitoring is set out in the annual National Residue Control Plan, which is approved by the European Commission, and is an important component of the DAFM food safety controls and is implemented under a service contract with the Food Safety Authority of Ireland. Since 1999, the Marine Institute has implemented the National Residues Monitoring Programme for aquaculture. This is carried out on behalf of the Sea Fisheries Protection Authority, which is the responsible organisation for residue controls on farmed finfish. In 2021, in excess of 632 tests and a total of 1,870 measurements were carried out on 120 samples of farmed finfish for a range of residues. Implementation of the Aquaculture 2021 Plan involves taking samples at both farm and processing plant: *80 target samples taken at harvest: 70 farmed salmon and 10 freshwater trout. *40 target samples were taken at other stages of production: 30 salmon smolts and 10 freshwater trout. All 2021 samples were compliant. For target sampling of farmed fish, a summary table of the residue results from 2005 - 2021 is outlined in Table 1. Overall, the outcome for aquaculture remains one of consistently low occurrence of residues in farmed finfish, with no non-compliant target residues results for the period 2006-2014, 0.11% and 0.10% non-compliant target residues results in 2015 and 2016 respectively and no non-compliant target results for the period 2017 to 2021