Online elemental analysis of process gases with ICP-OES: A case study on waste wood combustion

A mobile sampling and measurement system for the analysis of gaseous and liquid samples in the field was developed. An inductively coupled plasma optical emission spectrometer (ICP-OES), which is built into a van, was used as detector. The analytical system was calibrated with liquid and/or gaseous standards. It was shown that identical mass flows of either gaseous or liquid standards resulted in identical ICP-OES signal intensities. In a field measurement campaign trace and minor elements in the raw flue gas of a waste wood combustor were monitored. Sampling was performed with a highly transport efficient liquid quench system, which allowed to observe temporal variations in the elemental process gas composition. After a change in feedstock an immediate change of the element concentrations in the flue gas was detected. A comparison of the average element concentrations during the combustion of the two feedstocks showed a high reproducibility for matrix elements that are expected to be present in similar concentrations. On the other hand elements that showed strong differences in their concentration in the feedstock were also represented by a higher concentration in the flue gas. Following the temporal variations of different elements revealed strong correlations between a number of elements, such as chlorine with sodium, potassium and zinc, as well as arsenic with lead, and calcium with strontium.     

From safety culture to safety orientation: Validation and simplification of a safety orientation scale using a sample of seafarers working for Norwegian ship owners

Measuring safety performance is becoming increasingly important in many high-risk industries such as atomic power, the chemical industry, offshore oil production, air traffic control and construction. Much has been done to study the antecedents/factors that shape the safety culture and safety climate in these types of industries, but almost no research has been conducted into another high-risk industry – shipping. Based on the safety orientation model (SOM) and a review of items and scales used in surveys of safety climate and safety culture, a safety orientation scale (SOS) was developed and refined through the use of multivariate statistics. This study was conducted with a sample of seafarers sailing on Norwegian-owned vessels. A total of 2558 questionnaires were returned from 141 vessels and 16 shipping companies, giving a calculated response rate of 70%.The study showed that replicating previous studies on the sample of seafarers demonstrated a large degree of stability in scales and items across both industries and nations.Exploratory factor analysis (EFA) is the most commonly adopted approach to the development of scales of safety climate and culture scale reported in the literature, and factor retention seems to be the most important decision in EFA. In the present study several rules to determine the number of factors and items retained are applied, and a comparison is made of a short form of latent root criterion (SFLRC) and parallel criterion (PC). SFLRC is found to be the superior method for the present data set.Confirmatory factor analysis (CFA) did not support the preliminary SOM of 12 dimensions (13 dimensions, since one of the 12 dimensions was split during the CFA procedure); however, a re-specification of the model on the basis of the CFA for four different behavioural measures gave a simplified and well-defined model with seven factors and 22 items.     

Assessing the value of CO2 capture ready in new-build pulverised coal-fired power plants in China

Making new plants CO₂ capture ready (CCR) would enable them to retrofit to capture CO₂ at a later date at lower cost when the appropriate policy and/or economic drivers are in place. In order to understand the economic value and investment characteristics of making new plants CCR in China, a typical 600 MW pulverised coal-fired ultra-supercritical power plant, locating in Guangdong province, was examined. Combined with an engineering assessment, costs were estimated for different CCR scenarios. To analyze CCR investment opportunities, the paper applies a cash flow model for valuing capture options and CCR investment. Results were obtained by Monte-Carlo simulation, based on engineering surveys and an IEA GHG CCR study, as well as plant performance information and expert projections on carbon prices, coal prices and electricity prices.CCR investments are justified by factors such as higher retrofitting probabilities, lower early closure probabilities and fair economic return. However, the economic case for CCR largely depends on two factors: (a) whether the original plant is retrofittable without CCR; and (b) the type of investments made, for example, investments essential to CCR tend to be more economic than additional non-essential CCR features such as clutched low pressure turbines. The carbon price and discount rate were found to have significant impacts on the economics of CCR. Overall, it appears that the value of the ‘capture options’ that CCR generates for retrofitting CCS is significant, and so could justify a modest CCR investment, even assuming the original plant is retrofittable without CCR. It was also found the value of CCR might be significantly understated if the range of potential retrofitting dates is artificially constrained.     

A Practical Guide to Estimating Cleanup Costs

Cost estimates are frequently developed to evaluate hazardous‐waste‐site cleanup options in support of a site investigation, remedy selection decision, or assessment of environmental liabilities. The accuracy of the cost estimate depends largely on the quality of the information available at the time it is prepared. This article presents a practical guide to developing a cleanup cost estimate. It includes information on how to document assumptions, use the latest technical resources, and perform basic adjustments to account for uncertainty and the time value of money. The content is based upon a recent guidance document issued by the U.S. Environmental Protection Agency and U.S. Army Corps of Engineers entitled A Guide to Developing and Documenting Cost Estimates during the Feasibility Study (USEPA, 2000). © 2001 John Wiley & Sons, Inc.     

Synthesis of fluorinated polybrominated diphenyl ethers (F-PBDEs) as internal standards for environmental analysis

Polybrominated diphenyl ethers (PBDEs) have become widely distributed as environmental contaminants due to their wide-spread use as flame retardants. Their structural similarity to other halogenated organic pollutants, for example polychlorinated biphenyls (PCBs), has led to speculation that they may have similar toxicological properties and effects. Recent focus on PBDEs as possible priority pollutants has also led to an increasing need for reference standards of PBDEs for toxicological studies and for environmental analysis. In this work we synthesized a series of fluorinated PBDEs (F-PBDEs) which can be used as possible internal standards, as an alternative to high-cost alternatives, such as the (13)C-labelled analogues. F-PBDEs have been synthesized by using different coupling reactions and by bromination of fluorinated starting materials.     

A Biomimetic Approach to the Detection and Identification of Estrogen Receptor Agonists in Surface Waters Using Semipermeable Membrane Devices (SPMDs) and Bioassay-Directed Chemical Analysis (12 pp)

Goal, Scope and Background Some anthropogenic pollutants posses the capacity to disrupt endogenous control of developmental and reproductive processes in aquatic biota by activating estrogen receptors. Many anthropogenic estrogen receptor agonists (ERAs) are hydrophobic and will therefore readily partition into the abiotic organic carbon phases present in natural waters. This partitioning process effectively reduces the proportion of ERAs readily available for bioconcentration by aquatic biota. Results from some studies have suggested that for many aquatic species, bioconcentration of the freely-dissolved fraction may be the principal route of uptake for hydrophobic pollutants with logarithm n-octanol/water partition coefficient (log Kow) values less than approximately 6.0, which includes the majority of known anthropogenic ERAs. The detection and identification of freely-dissolved readily bioconcentratable ERAs is therefore an important aspect of exposure and risk assessment. However, most studies use conventional techniques to sample total ERA concentrations and in doing so frequently fail to account for bioconcentration of the freely-dissolved fraction. The aim of the current study was to couple the biomimetic sampling properties of semipermeable membrane devices (SPMDs) to a bioassay-directed chemical analysis (BDCA) scheme for the detection and identification of readily bioconcentratable ERAs in surface waters. Methods SPMDs were constructed and deployed at a number of sites in Germany and the UK. Following the dialytic recovery of target compounds and size exclusion chromatographic clean-up, SPMD samples were fractionated using a reverse-phase HPLC method calibrated to provide an estimation of target analyte log Kow. A portion of each HPLC fraction was then subjected to the yeast estrogen screen (YES) to determine estrogenic potential. Results were plotted in the form of 'estrograms' which displayed profiles of estrogenic potential as a function of HPLC retention time (i.e. hydrophobicity) for each of the samples. Where significant activity was elicited in the YES, the remaining portion of the respective active fraction was subjected to GC-MS analysis in an attempt to identify the ERAs present. Results and Discussion Estrograms from each of the field samples showed that readily bioconcentratable ERAs were present at each of the sampling sites. Estimated log Kow values for the various active fractions ranged from 1.92 to 8.63. For some samples, estrogenic potential was associated with a relatively narrow range of log Kow values whilst in others estrogenic potential was more widely distributed across the respective estrograms. ERAs identified in active fractions included some benzophenones, various nonylphenol isomers, benzyl butyl phthalate, dehydroabietic acid, sitosterol, 3-(4-methylbenzylidine)camphor (4-MBC) and 6-acetyl-1,1,2,4,4,7-hexamethyltetralin (AHTN). Other tentatively identified compounds which may have contributed to the observed YES activity included various polycyclic aromatic hydrocarbons (PAHs) and their alkylated derivatives, methylated benzylphenols, various alkylphenols and dialkylphenols. However, potential ERAs present in some active fractions remain unidentified. Conclusions and Outlook Our results show that SPMD-YES-based BDCA can be used to detect and identify readily bioconcentratable ERAs in surface waters. As such, this biomimetic approach can be employed as an alternative to conventional methodologies to provide investigators with a more environmentally relevant insight into the distribution and identity of ERAs in surface waters. The use of alternative bioassays also has the potential to expand SPMD-based BDCA to include a wide range of toxicological endpoints. Improvements to the analytical methodology used to identify ERAs or other target compounds in active fractions in the current study could greatly enhance the applicability of the methodology to risk assessment and monitoring programmes.     

The valuation of forest carbon services by Mexican citizens: the case of Guadalajara city and La Primavera biosphere reserve

Adequate demand for, and recognition of, forest carbon services is critical to success of market mechanisms for forestry-based conservation and climate change mitigation. National and voluntary carbon-offsetting schemes are emerging as alternatives to international compliance markets. We developed a choice experiment to explore determinants of local forest carbon-offset valuation. A total of 963 citizens from Guadalajara in Mexico were asked to consider a purchase of voluntary offsets from the neighbouring Biosphere Reserve of La Primavera and from two alternative more distant locations: La Michilía in the state of Durango and El Cielo in Tamaulipas. Surveys were applied in market stall sessions and online using two different sampling methods: the snowball technique and via a market research company. The local La Primavera site attracted higher participation and valuation than the more distant sites. However, groups particularly interested in climate change mitigation or cost may accept cost-efficient options in the distant sites. Mean implicit carbon prices obtained ranged from $6.79 to $15.67/tCO_2eq depending on the surveying methodology and profile of respondents. Survey application mode can significantly affect outcome of the experiment. Values from the market stall sessions were higher than those from the snowball and market research samples obtained online; this may be linked to greater cooperation associated with personal interaction and collective action. In agreement with the literature, we found that valuation of forest carbon offsets is associated with cognitive, ethical, behavioural, geographical and economic factors.