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Maximizing automation in LC/MS high-throughput analysis and purification.

Here, we describe a system for LC/MS-based analysis and purification of compounds aiming at the minimization of manual interference in the overall process. Key elements of the concept are automated identification of the target compounds, automated assignment of optimized preparative gradients for purification of the target compounds, and automated purity assessment of fractions with subsequent pooling of validated product fractions. Additional support is provided by an automated solvent and waste management system. One person can easily process 100-200 compounds on a 150-mg scale per day on that system, while still the maximization of purity and yield after purification is guaranteed. Reduced demands with respect to purity or yield can lead to significantly higher throughput numbers.

Automation↗

Low molecular weight carboxylic acids in oxidizing porphyry copper tailings.

The distribution of low molecular weight carboxylic acids (LMWCA) was investigated in pore water profiles from two porphyry copper tailings impoundments in Chile (Piuquenes at La Andina and Cauquenes at El Teniente mine). The objectives of this study were (1) to determine the distribution of LMWCA, which are interpreted to be the metabolic byproducts of the autotroph microbial community in this low organic carbon system, and (2) to infer the potential role of these acids in cycling of Fe and other elements in the tailings impoundments. The speciation and mobility of iron, and potential for the release of H+ via hydrolysis of the ferric iron, are key factors in the formation of acid mine drainage in sulfidic mine wastes. In the low-pH oxidation zone of the Piuquenes tailings, Fe(III) is the dominant iron species and shows high mobility. LMWCA, which occur mainly between the oxidation front down to 300 cm below the tailings surface at both locations (e.g., max concentrations of 0.12 mmol/L formate, 0.17 mmol/L acetate, and 0.01 mmol/L pyruvate at Piuquenes and 0.14 mmol/L formate, 0.14 mmol/L acetate, and 0.006 mmol/L pyruvate at Cauquenes), are observed at the same location as high Fe concentrations (up to 71.2 mmol/L Fe(II) and 16.1 mmol/L Fe(III), respectively). In this zone, secondary Fe(III) hydroxides are depleted. Our data suggest that LMWCA may influence the mobility of iron in two ways. First, complexation of Fe(III), through formation of bidentate Fe(III)-LMWCA complexes (e.g., pyruvate, oxalate), may enhance the dissolution of Fe(III) (oxy)hydroxides or may prevent precipitation of Fe(III) (oxy)hydroxides. Soluble Fe(III) chelate complexes which may be mobilized downward and convert to Fe(II) by Fe(III) reducing bacteria. Second, monodentate LMWCA (e.g., acetate and formate) can be used by iron-reducing bacteria as electron donors (e.g., Acidophilum spp.), with ferric iron as the electron acceptor. These processes may, in part, explain the low abundances of secondary Fe(III) hydroxide precipitates below the oxidation front and the high concentrations of Fe(II) observed in the pore waters of some low-sulfide systems. The reduction of Fe(III) and the subsequent increase of iron mobility and potential acidity transfer (Fe(II) oxidation can result in the release of H+ in an oxic environment) should be taken in account in mine waste management strategies.

Acetates↗

The first structural and spectroscopic characterization of a neptunyl polyoxometalate complex.

The reaction between PW9O349- and NpO2+ has yielded the first structurally characterized neptunyl(V) polyoxometalate complex, [Na2(NpO2)2(A-PW9O34)2]14-. This complex is isostructural with the uranyl(VI) analogue, and there is also spectroscopic evidence for its existence in solution. The complex is readily extracted into toluene, and this may have significance in the sequestering and/or separation of the neptunyl ion in terms of nuclear waste management.

Journal Article↗

Molecular dynamics study of the hydration of lanthanum(III) and europium(III) including many-body effects.

Lanthanides complexes are widely used as contrast agents in magnetic resonance imaging (MRI) and are involved in many fields such as organic synthesis, catalysis, and nuclear waste management. The complexation of the ion by the solvent or an organic ligand and the resulting properties (for example the relaxivity in MRI) are mainly governed by the structure and dynamics of the coordination shells. All of the MD approaches already carried out for the lanthanide(III) hydration failed due to the lack of accurate representation of many-body effects. We present the first molecular dynamics simulation including these effects that accounts for the experimental results from a structural and dynamic (water exchange rate) point of view.

Letter↗

Genitourinary issues during spaceflight: a review.

The genitourinary (GU) system is not uncommonly affected during previous spaceflights. GU issues that have been observed during spaceflight include urinary calculi, infections, retention, waste management, and reproductive. In-flight countermeasures for each of these issues are being developed to reduce the likelihood of adverse sequelae, due to GU issues during exploration-class spaceflight, to begin in 2018 with flights back to the Moon and on to Mars, according to the February 2004 Presendent's Vision for US Space Exploration. With implementation of a robust countermeasures program, GU issues should not have a significant threat for mission impact during future spaceflights.

Aerospace Medicine↗

Survival of Escherichia coli O157 in abattoir waste products.

AIMS: This study monitored survival and growth of Escherichia coli O157 in ovine and bovine abattoir waste. METHODS: Blood and gut contents were inoculated separately with cocktails of E. coli O157. Samples were stored aerophilically and microaerophilically at 5 degrees C, 15 degrees C and 30 degrees C to represent storage at different container depths and at extremes of UK ambient temperature. CONCLUSIONS: Results showed survival of E. coli O157 was irrespective of oxygen content with no significant differences observed between aerophilic and microaerophilic environments. Numbers of E. coli O157 in ovine and bovine gut contents showed no change when stored at 5 degrees C and increased 1-2 log(10) at 15 degrees C and 30 degrees C in 28 h. In ovine and bovine blood, irrespective of storage temperature, there was a 0.5-2 log(10) reduction or no change in numbers except in ovine blood stored at 30 degrees C where the fall in numbers was followed by a 3 log(10) increase. In aged (stored at 4 degrees C for 18 h before spiking) bovine blood there was no significant change in numbers at 5 degrees C while at 15 degrees C there was 2 log(10) rise after 48 h. At 30 degrees C there was an initial 1 log(10) decrease in numbers followed by a 1 log(10) rise over the following 40 h. SIGNIFICANCE AND IMPACT OF STUDY: Abattoir wastes may become contaminated from animals infected with Verocytotoxigenic E. coli O157 and in certain storage conditions these pathogens could significantly increase in numbers. There is need for care in abattoir waste disposal, not only for personnel subject to direct contact, but also in the prevention of cross contamination to adjacent land and water courses which could indirectly infect humans.

Abattoirs↗

Swine wastewater treatment by media filtration.

A media filter was constructed to treat swine wastewater after anaerobic lagoon treatment. The media filter consisted of a tank (1.5-m-diameter x 0.6-m-height) filled with marl gravel. The marl gravel had a carbonate content of 300 g kg-1. Gravel particle size distributions were 85 and 14% in the 4.7- to 12.7-mm and 12.7- to 19-mm size classes, respectively. Pore space of the filtration unit was 57%. Wastewater flow rate was 606 L m-2 d-1, and total Kjeldahl nitrogen (TKN) load was 198 g m-2 d-1. The media filter removed 54% of chemical oxygen demand (COD) content after one cycle, but increased cycling did not produce additional COD reduction. Total suspended solids (TSS) removal after one cycle was 50% of initial levels, and additional cycling reduced TSS levels at a much lower rate of 7% per cycle. Removal efficiencies for total phosphorus (TP) ranged from 37% to 52% (one to four cycles), but long-term phosphorus removal would be limited by the sorption capacity of the gravel. Up to 24% of TKN was converted to nitrate-plus-nitrite-N (NO3+NO2-N). Effluents with high NO3+NO2-N levels can be treated further for denitrification with constructed wetlands or anaerobic lagoon. This is important in cases where land is limited for wastewater application.

Agriculture↗

Microbial CO conversions with applications in synthesis gas purification and bio-desulfurization.

Recent advances in the field of microbial physiology demonstrate that carbon monoxide is a readily used substrate by a wide variety of anaerobic micro-organisms, and may be employed in novel biotechnological processes for production of bulk and fine chemicals or in biological treatment of waste streams. Synthesis gas produced from fossil fuels or biomass is rich in hydrogen and carbon monoxide. Conversion of carbon monoxide to hydrogen allows use of synthesis gas in existing hydrogen utilizing processes and is interesting in view of a transition from hydrogen production from fossil fuels to sustainable (CO2-neutral) biomass. The conversion of CO with H2O to CO2 and H2 is catalyzed by a rapidly increasing group of micro-organisms. Hydrogen is a preferred electron donor in biotechnological desulfurization ofwastewaters and flue gases. Additionally, CO is a good alternative electron donor considering the recent isolation of a CO oxidizing, sulfate reducing bacterium. Here we review CO utilization by various anaerobic micro-organisms and their possible role in biotechnological processes, with a focus on hydrogen production and bio-desulfurization.

Bacteria, Anaerobic↗

Engineering strontium binding affinity in an EF-hand motif: a quantum chemical and molecular dynamics study.

Proteins with the ability to specifically bind strontium would potentially be of great use in the field of nuclear waste management. Unfortunately, no such peptides or proteins are known -- indeed, it is uncertain whether they exist under natural conditions due to low environmental concentrations of strontium. To investigate the possibility of devising such molecules, one of us (CV), in a previous experimental study, proposed starting from an EF-hand motif of the protein calmodulin and mutating some residues to change the motif's specificity for calcium into one for strontium. In this paper, which represents a theoretical complement to the experimental work, we analyzed small-molecule crystallographic structures and performed quantum chemical calculations to identify possible mutations. We then constructed seven mutant sequences of the EF-hand motif and analyzed their dynamical and binding behaviors using molecular dynamics simulations and free-energy calculations (using the MM/PBSA method). As a result of these analyzes we were able to isolate some characteristics that could lead to mutant peptides with enhanced strontium affinity.

Amino Acid Motifs↗

Summary of the 1989 EPA/A&WMA International symposium: measurement of toxic and related air pollutants.

A joint conference, for the fourth straight year cosponsored by the Air & Waste Management Association's TP-6, TP-7, and ITF-2 technical committees, and the Atmospheric Research and Exposure Assessment Laboratory of the U.S. Environmental Protection Agency, was held at Raleigh, North Carolina, May 2-5, 1989. The technical program consisted of 145 presentations, held in 14 separate technical sessions, on recent advances in the measurement and monitoring of toxic and related pollutants found in ambient and source atmospheres. Covering a wide range of measurement topics and superbly supported by 57 exhibitors of instrumentation and consulting services, the symposium was enthusiastically received by more than 700 attendees from the United States and other countries. This overview contains a selection of the highlights from the technical presentations. A synopsis of the keynote address to the symposium is also included.

Air Pollutants↗

Novel approach to analyzing the carcinogenic effect of ionizing radiations.

PURPOSE: Cancer incidence of ionizing radiations exposure is considered to be proportional to the absorbed dose. However, there are disagreements between substantial amounts of epidemiological studies. In this study, we question the basic relationship of the risk estimate with total accumulated dose, and reanalyse available data on the basis of a daily dose concept. MATERIALS AND METHODS: The data analysed were relative mortality risk from all cancers vs. total-body dose on a daily basis. References have been selected on the basis of objective criteria. RESULTS: We found that this relationship removes major discrepancies. It revises estimates of low-level exposures, with consequences regarding nuclear power plants safety, wastes management, medical applications or homeland security. CONCLUSIONS: The idea that the dose rate may have a significant impact on health effects of ionizing radiations is not new, but has always been considered as a parameter in models based on integrated dose. The novel approach in this paper is to consider the primary relevant parameter as an average of dose rate over a time period of one day. This is an argument to revise the whole philosophy in radioprotection, and place regulatory limits on specific locations instead of annual limits relevant to individual persons.

Humans↗

The appropriateness of Multicriteria Analysis in environmental decision-making problems.

Environmental decision-making occurs in numerous environmental sectors and covers a diverse range of problems. Of the various decision tools available not all of them may be appropriate for any single decision problem, and any particular decision-aid may not be applicable in all decision problems. This article reviews applications of MCA, and considers the appropriateness of Multicriteria Analysis (MCA) in environmental decision-making problems. Due to natural and decision environments being multidimensional, environmental decision-making is characterized by complexity. Consequently MCA has commonly been used in this area. In Environmental Impact Assessment (EIA) the multiple dimensions of the impacts evaluated have been easily represented in MCA as multiple criteria. Waste management and water resource planning problems involving public participation have been facilitated by MCA, through the structuring and articulation of the public's values. MCA has also been applied in water quality problems, allowing the incorporation of incommensurable criteria into evaluations. The appropriateness of MCA for environmental decision problems can be viewed in the context of a typical decision-making process, making it easier to identify the contribution MCA can make at various decision-making stages. MCA can be particularly appropriate when the decision-making context is characterized by multiple objectives and multiple criteria, incommensurable criteria, mixed data and the need for ease of use, and the analysis context is characterized by multiple participants.

Conservation of Natural Resources↗

Health and social benefits from improving community hygiene and sanitation: an Indian experience.

India is a country where Atomic Age and near Stone Age people co-exist. On one hand India has achieved development in many areas, but on the other hand there is still the practice of open defecation and manual cleaning of human excreta from bucket privies by scavengers. National sanitation coverage is only about 34% meaning that 66% of the population practises open defecation. Such unhygienic conditions lead to infections and high mortality and morbidity in the community. Low sanitation coverage could be due to lack of affordable sanitation technology and awareness or motivation. Although the sewerage system was introduced in India long ago, high operational and maintenance costs have prohibited it from being implemented in most towns and cities. Similarly, the cost of a septic tank is beyond most people, and disposal of undigested sludge from septic tanks remains a problem. In contrast, the pour-flush two-pit toilet (known as Sulabh Shauchalaya) is a low cost, socially acceptable and appropriate technology that does not require scavengers to clean the pits. Sulabh has converted and constructed over 1.2 million such toilets throughout India, making 240 towns scavenger-free. Liberated scavengers are thereby available to take up vocational training in various market-oriented trades enabling self-employment. The on-site/ decentralised systems of waste management has improved community health and hygiene, particularly in socially deprived groups, and reduced the financial burden of local government.

Defecation↗

Landfill gas effects on groundwater samples at a municipal solid waste facility.

A study was performed to determine the source of low concentrations of volatile organic compounds (VOCs) detected in groundwater samples at a solid waste management facility. The affected wells were identified as hydraulically upgradient of an old unlined facility, but downgradient of a new clay-lined landfill. These monitoring wells are close to both sites. Subsurface landfill gas migration was identified after a low permeability cap was installed on the older site. Subsurface gas pressure was monitored to identify horizontal landfill gas migration. Monitoring well headspace gases were evaluated to identify depressed oxygen concentrations and methane because of landfill gas migration into the well. Monitoring well headspace gas VOC concentrations were compared to groundwater VOC concentrations to determine the direction of phase transfer. A ratio above 1.0 of the observed well headspace gas concentration of a VOC to the concentration that would be in equilibrium with the groundwater concentration indicates gas-to-water phase transfer within the well. For the major gas-phase and aqueous-phase VOC, cis-1,2-dichloroethene, gas-to-water phase transfer is clearly indicated from the data for two of the four wells. Fifteen other VOCs were detected in monitoring well headspace gases but not in groundwater samples from the four wells studied. Only one compound in one well was detected in the groundwater sample but not in the headspace gases, and only one compound in one well was detected in both matrices at concentrations that suggested water-to-gas phase transfer. This study suggests that if landfill gas is suspected as the source of detected VOCs, monitoring well construction and stratigraphy are important considerations when attempting to differentiate between groundwater contamination by landfill gas and contamination from other sources.

Environmental Monitoring↗

Release of mercury from broken fluorescent bulbs.

Mercury is a persistent, bioaccumulative toxin. Although the primary human exposure is from ingestion of fish contaminated with methyl mercury (HgCH3), exposures to elemental mercury vapor and mercury compounds via inhalation and dermal contact may also occur. Fluorescent bulbs contain mercury. Estimates of the amount of this mercury released when the bulbs are discarded and broken have varied widely. A new method was developed for measuring mercury released from broken bulbs. With the assumption that all mercury released is elemental vapor, it was found that between 17 and 40% of the mercury in broken low-mercury fluorescent bulbs is released to the air during a two-week period immediately following breakage, with higher temperatures contributing to higher release rates. One-third of the mercury release occurs during the first 8 hr after breakage. Many bulbs contain more mercury than the low-mercury bulbs tested. A typical discarded bulb releases between 3 and 8 mg of elemental mercury vapor over two weeks. Approximately 620 million fluorescent bulbs are discarded annually in the United States, and many are broken during disposal. Based on the estimated release rate of 3-8 mg per broken bulb developed in this study, discarded bulbs release approximately 2-4 tons of mercury per year in the United States. Waste management systems that minimize breakage before final disposal could reduce this total, as would the reduction of mercury content of bulbs. Elevated airborne levels of mercury could exist in the vicinity of recently broken bulbs, and under certain conditions, mercury concentrations could exceed occupational exposure limits.

Environmental Monitoring↗

Toxicological evaluation for the hazard assessment of tire crumb for use in public playgrounds.

Disposal of used tires has been a major problem in solid waste management. New uses will have to be found to consume recycled tire products. One such proposed use is as ground cover in playgrounds. However, concern has been expressed regarding exposure of children to hazardous chemicals and the environmental impact of such chemicals. We designed a comprehensive hazard assessment to evaluate and address potential human health and environmental concerns associated with the use of tire crumb in playgrounds. Human health concerns were addressed using conventional hazard analyses, mutagenicity assays, and aquatic toxicity tests of extracted tire crumb. Hazard to children appears to be minimal. Toxicity to all aquatic organisms (bacteria, invertebrates, fish, and green algae) was observed; however, this activity disappeared with aging of the tire crumb for three months in place in the playground. We conclude that the use of tire crumb in playgrounds results in minimal hazard to children and the receiving environment.

Animals↗

Recycling in a megacity.

In the aftermath of the 9/11 disaster, Mayor Bloomberg of New York City unveiled an aggressive budget plan that included the temporary suspension of glass and plastics recycling. This was considered by many to be anti-environmental, but the results of this study show that for lack of markets, even at zero or negative prices, nearly 90% of the plastic and glass set aside by thoughtful New Yorkers was transported to materials recovery facilities (MRFs) and from there to landfills. Sending bales of plastics to landfills is not limited to New York City. It is an environmental paradox that the United States is digging up new oil fields in pristine areas and, at the same time, continues to convert greenfields to brownfields by burying nearly 20 million tons of plastic fuel annually. The study also determined that at the present rate of source separation, estimated to be less than 30% of the available recyclables in 1999, building large, modern MRFs may increase substantially the rate of New York City recycling and also allow single-stream collection of commingled recyclables, as is done in Phoenix, AZ. Single-stream collection simplifies separation at the source by citizens and increases the amount of collected recyclables. Also, because collection represents a large fraction of the costs of waste management, it may have a significant economic advantage.

Commerce↗