Recovery of Homogeneous Platinoid Catalysts from Pharmaceutical Media: Review on the Existing Treatments and the Perspectives of Membrane Processes.

Catalyst recovery is a major challenge for reaching the objectives of green chemistry for industry. Indeed, catalysts enable quick and selective syntheses with high reaction yields. This is especially the case for homogeneous platinoid catalysts which are almost indispensable for cross-coupling reactions often used by the pharmaceutical industry. However, they are based on scarce, expensive, and toxic resources. In addition, they are quite sensitive and degrade over time at the end of the reaction. Once degraded, their regeneration is complex and hazardous to implement. Working on their recovery could lead to highly effective catalytic chemistries while limiting the environmental and economic impacts of their one-time uses. This review aims to describe and compare conventional processes for metal removal while discussing their advantages and drawbacks considering the objective of homogeneous catalyst recovery. Most of them lead to difficulty recycling active catalysts due to their ability to only treat metal ions or to chelate catalysts without the possibility to reverse the mechanism. However, membrane processes seem to offer some perspectives with limiting degradations. While membranes are not systematically the best option for recycling homogeneous catalysts, current development might help improve the separation between pharmaceutical active ingredients and catalysts and enable their recycling.

On-Line NIR to Regulate Pervaporation Process: Application for Dehydration.

The regeneration of volatile organic solvents via dehydration tests, from 90 wt %, was evaluated by pervaporation using an on-line near-infrared (NIR) spectrometer. Experiments were performed using a bis(triethoxysilyl)methane (BTESM)-based ceramic HybSi® membrane at temperatures of 20, 30 and 40 °C. The presence of an on-line NIR allows continuous monitoring of the process without sampling, and quickly estimates mass fractions of species in the retentate. Dehydration tests were performed at 30 °C in order to confirm the on-line NIR reproducibility, and closely matched results obtained with an off-line densimeter. These results validated the usefulness of the on-line NIR and provided the same precision whatever the mass fraction in the retentate. A good on-line reproducibility was found, with an agreement between the on-line NIR and off-line densimeter, obtaining an average deviation of ±0.058 wt %, ±0.17 wt % and ±0.049 wt %, respectively, at 20, 30 and 40 °C.

Measurement of fine particulate matter water-soluble inorganic species and precursor gases in the Alberta Oil Sands Region using an improved semicontinuous monitor.

UNLABELLED: The ambient ion monitor-ion chromatography (AIM-IC) system, which provides hourly measurements of the main chemical components of PM2.5 (particulate matter with an aerodynamic diameter<2.5 µm) and its precursor gases, was evaluated and deployed from May to July 2011 and April to December 2013 in the Athabasca Oil Sands Region (AOSR) of northeastern Alberta, Canada. The collection efficiencies for the gas-phase SO2 and HNO3 using the cellulose membrane were 96% and 100%, respectively, and the collection efficiency of NH3 using the nylon membrane was 100%. The AIM-IC was compared with a collocated annular denuder sampling system (ADSS) and a Federal Reference Method (FRM) Partisol PM2.5 sampler. The correlation coefficients of SO4(2-) concentrations between the AIM-IC and ADSS and between the AIM-IC and the Partisol PM2.5 sampler were 0.98 and 0.95, respectively. The comparisons also showed no statistically significant difference between the measurement sets, suggesting that the AIM-IC measurements of the PM2.5 chemical composition are comparable to the ADSS and Partisol PM2.5 methods. NH3 concentration in the summer (mean±standard deviation, 1.9±0.7 µg m(-3)) was higher than in the winter (1.3±0.9 µg m(-3)). HNO3 and NO3- concentrations were generally low in the AOSR, and especially in the winter months. NH4+ (0.94±0.96 µg m(-3)) and SO4(2-) (0.58±0.93 µg m(-3)) were the major ionic species of PM2.5. Direct SO2 emissions from oil sands processing operations influenced ambient particulate NH4+ and SO4(2-) values, with hourly concentrations of NH4+ and SO4(2-) measured downwind (~30 km away from the stack) at 10 and 28 µg m(-3). During the regional forest fire event in 2011, high concentrations of NO3-, NH4+, HNO3, NH3, and PM2.5 were observed and the corresponding maximum hourly concentrations were 31, 15, 9.6, 89, and >450 (the upper limit of PM2.5 measurement) µg m(-3), suggesting the formation of NH4NO3. IMPLICATIONS: The AOSR in Canada is one of the most scrutinized industrial regions in the developed world due to the extent of oil extraction activities. Because of this, it is important to accurately assess the effect of these operations on regional air quality. In this study, we compare a new analytical approach, AIM-IC, with more standard analytical approaches to understand how local anthropogenic and nonanthropogenic sources (e.g., forest fires) impact regional air quality. With this approach, we also better characterize PM2.5 composition and its precursor gases to understand secondary aerosol formation mechanisms and to better identify possible control techniques if needed.

Mercury in northeastern North America: a synthesis of existing databases.

A large number of datasets representing mercury (Hg) levels in northeastern North America were assembled in a standardized format between 2000 and 2003. Based on support from the Northeastern States Research Cooperative, scientists annually gathered and developed an operational template to collaboratively analyze and interpret these data for a series of peer-reviewed publications. The diverse group covered Hg policy connections, Hg in air, sediment and surface water, Hg in biota, and Hg collection, assessment and monitoring tools. A site-specific application of these Hg data is provided to demonstrate the importance of well-placed air monitoring stations, the need for integrative multimedia data sets, and the complexity of linking abiotic and biotic Hg compartments. Demonstrated is the ubiquitous nature of Hg and methylmercury availability and how its heterogeneous distribution is now relatively well understood for northeastern North America.

Factors influencing mercury in freshwater surface sediments of northeastern North America.

We report on an inventory and analysis of sediment mercury (Hg) concentrations from 579 sites across northeastern North America. Sediment Hg concentrations ranged from the limit of detection ca. 0.01-3.7 microg g(-1) (dry weight, d.w.), and the average concentration was 0.19 microg g(-1) (d.w.) Sediment methylmercury concentrations ranged from 0.15 to 21 ng g(-1) (d.w.) and the mean concentration was 3.83 ng g(-1) (d.w.). Total Hg concentrations (HgT) were greatest in lakes > reservoirs > rivers, although the proportion of Hg as methylmercury showed an inverse pattern. Total Hg was weakly and positively correlated with the sediment organic matter and percent of watershed as forested land, and weakly and negatively correlated with sediment solids content, drainage area, and agricultural land. Sediment methylmercury concentrations were weakly and positively correlated to wetland area, and weakly and negatively correlated to drainage area. Methylmercury, expressed as a percentage of HgT was positively correlated to agricultural land area. For sites with co-located sediment and fish-tissue sampling results, there was no relationship between sediment Hg and fish-tissue Hg. Finally, our data indicate that at least 44% of waters across the region have sediment HgT concentrations in excess of Canadian and United States minimum sediment contaminant guidelines for the protection of aquatic biota.

Distribution patterns of mercury in lakes and rivers of northeastern North America.

We assembled 831 data points for total mercury (Hg(t)) and 277 overlapping points for methyl mercury (CH3Hg+) in surface waters from Massachussetts, USA to the Island of Newfoundland, Canada from State, Provincial, and Federal government databases. These geographically indexed values were used to determine: (a) if large-scale spatial distribution patterns existed and (b) whether there were significant relationships between the two main forms of aquatic Hg as well as with total organic carbon (TOC), a well know complexer of metals. We analyzed the catchments where samples were collected using a Geographical Information System (GIS) approach, calculating catchment sizes, mean slope, and mean wetness index. Our results show two main spatial distribution patterns. We detected loci of high Hg(t) values near urbanized regions of Boston MA and Portland ME. However, except for one unexplained exception, the highest Hg(t) and CH3Hg+ concentrations were located in regions far from obvious point sources. These correlated to topographically flat (and thus wet) areas that we relate to wetland abundances. We show that aquatic Hg(t) and CH3Hg+ concentrations are generally well correlated with TOC and with each other. Over the region, CH3Hg+ concentrations are typically approximately 15% of Hg(t). There is an exception in the Boston region where CH3Hg+ is low compared to the high Hg(t) values. This is probably due to the proximity of point sources of inorganic Hg and a lack of wetlands. We also attempted to predict Hg concentrations in water with statistical models using catchment features as variables. We were only able to produce statistically significant predictive models in some parts of regions due to the lack of suitable digital information, and because data ranges in some regions were too narrow for meaningful regression analyses.

Physical controls on total and methylmercury concentrations in streams and lakes of the northeastern USA.

The physical factors controlling total mercury (HgT) and methylmercury (MeHg) concentrations in lakes and streams of northeastern USA were assessed in a regional data set containing 693 HgT and 385 corresponding MeHg concentrations in surface waters. Multiple regression models using watershed characteristics and climatic variables explained 38% or less of the variance in HgT and MeHg. Land cover percentages and soil permeability generally provided modest predictive power. Percent wetlands alone explained 19% of the variance in MeHg in streams at low-flow, and it was the only significant (p < 0.02) predictor for MeHg in lakes, albeit explaining only 7% of the variance. When stream discharge was added as a variable it became the dominant predictor for HgT in streams, improving the model r2 from 0.19 to 0.38. Stream discharge improved the MeHg model more modestly, from r2 of 0.25 to 0.33. Methylation efficiency (MeHg/HgT) was modeled well (r2 of 0.78) when a seasonal term was incorporated (sine wave with annual period). Physical models explained 18% of the variance in fish Hg concentrations in 134 lakes and 55% in 20 reservoirs. Our results highlight the important role of seasonality and short-term hydrologic changes to the delivery of Hg to water bodies.

Assessing the recovery of lakes in southeastern Canada from the effects of acidic deposition.

Reductions in North American sulfur dioxide (SO2) emissions promoted expectations that aquatic ecosystems in southeastern Canada would soon recover from acidification. Only lakes located near smelters that have dramatically reduced emissions approach this expectation. Lakes in the Atlantic provinces, Quebec and Ontario affected only by long-range sources show a general decline in sulfate (SO4(2-)) concentrations, but with a relatively smaller compensating increase in pH or alkalinity. Several factors may contribute to the constrained (or most likely delayed) acidity response: declining base cation concentrations, drought-induced mobilization of SO4(2-), damaged internal alkalinity generation mechanisms, and perhaps increasing nitrate or organic anion levels. Monitoring to detect biological recovery in southeastern Canada is extremely limited, but where it occurs, there is little evidence of recovery outside of the Sudbury/Killarney area. Both the occurrence of Atlantic salmon in Nova Scotia rivers and the breeding success of Common Loons in Ontario lakes are in fact declining although factors beyond acidification also play a role. Chemical and biological models predict that much greater SO2 emission reductions than those presently required by legislation will be needed to promote widespread chemical and latterly, biological recovery. It may be unrealistic to expect that pre-industrial chemical and biological conditions can ever be reestablished in many lakes of southeastern Canada.