Sustainable fermentative hydrogen production: challenges for process optimisation

Over 160 publications related to fermentative hydrogen production from wastewater and solid wastes by mixed cultures are compiled and analyzed. Of the 98 reported cases, 57 used single substrates (mainly carbohydrates), 8 used actual wastewater, and 33 used solid wastes for hydrogen conversion. The key information is compiled in four tables: (1) pretreatment conditions for screening hydrogen-producing bacteria from anaerobic sludge or soil, and the process and performance parameters for (2) single substrates in synthetic wastewaters, (3) actual wastewaters, and (4) solid wastes. Process parameters discussed include pH, temperature, hydraulic retention time, seed sludge, nutrients, inhibitors, reactor design, and the means used for lowering hydrogen partial pressure. Performance parameters discussed include hydrogen yield, maximum volumetric production rate, maximum specific production rate, and conversion efficiency. The outlook for this new technology is discussed at the end.

Fermentative Hydrogen Production From Wastewater and Solid Wastes by Mixed Cultures

Hydrogen production from agricultural waste by dark fermentation: A review

This review highlights various aspects of current palladium membrane research and serves as a comprehensive bibliography covering palladium membrane preparation methods and applications. There are many promising uses for palladium membranes, although widespread use of the available technologies is constrained primarily by the high cost of palladium, lack of durability due to hydrogen embrittlement, and susceptibility to fouling. Various researchers in the field are tackling these problems and fabricating thinner palladium alloy composite membranes that better withstand contaminantion and thermal cycling. What has been accomplished to address these issues and the directions presently being explored are discussed.

Innovations in palladium membrane research

Fermentation of biomass or carbohydrate-based substrates presents a promising route of biological hydrogen production compared with photosynthetic or chemical routes. Pure substrates, including glucose, starch and cellulose, as well as different organic waste materials can be used for hydrogen fermentation. Among a large number of microbial species, strict anaerobes and facultative anaerobic chemoheterotrophs, such as clostridia and enteric bacteria, are efficient producers of hydrogen. Despite having a higher evolution rate of hydrogen, the yield of hydrogen [mol H2 (mol substrate(-1))] from fermentative processes is lower than that achieved using other methods; thus, the process is not economically viable in its present form. The pathways and experimental evidence cited in the literature reveal that a maximum of four mol of hydrogen can be obtained from substrates such as glucose. Modifications of the fermentation process, by redirection of metabolic pathways, gas sparging and maintaining a low partial pressure of hydrogen to make the reaction thermodynamically favorable, efficient product removal, optimum bioreactor design and integrating fermentative process with that of photosynthesis, are some of the ways that have been attempted to improve hydrogen productivity. This review briefly describes recent advances in these approaches towards improvement of hydrogen yield by fermentation.

Improvement of fermentative hydrogen production: various approaches.

Hydrogen production from organic waste

Quantification of volatile sulfur compounds in complex gaseous matrices by solid-phase microextraction.

A method was developed for the simultaneous determination of the following nine volatile sulfur compounds in gas samples: carbon disulfide, carbonyl sulfide, ethyl sulfide, ethyl methyl sulfide, hydrogen sulfide, isopropanethiol, methanethiol, methyl disulfide and methyl sulfide. The target compounds were preconcentrated by solid-phase microextraction (SPME) and determined by gas chromatography combined with mass spectrometry. Experimental design was employed to optimize the extraction time and temperature and concurrent detection of the nine compounds was achieved by using an SPME fiber coated with Carboxen-polydimethylsiloxane (75 μm). Detection limits ranged from 1 ppt (v/v) for carbon disulfide to 350 ppt (v/v) for hydrogen sulfide and calibration functions were linear up to 20 ppb (v/v) for all the compounds investigated.

Trace determination of volatile sulfur compounds by solid-phase microextraction and GC-MS

It has been shown that some of the fluorinated ethane derivatives being introduced as CFC-replacements can be transformed to TFA (trifluoroacetate) in the atmosphere. Moreover, TFA is extremely stable in the environment, and this has raised questions regarding how widespread TFA is in the environment. We found that TFA is ubiquitous in precipitation: samples of rain from Ireland and Poland and snow from Canada, Sweden, New Zealand, and East Antarctica contained 1-1100 ng/L, and, studying a firn core drilled in Antarctica, concentrations of 3-56 ng/L were measured in layers formed during the 19th century. We have confirmed the preindustrial presence of significant background concentrations of trifluoroacetate in historic precipitation samples from the analysis of firn. Extensive procedures were enforced to prevent sample contamination.It has been shown that some of the fluorinated ethane derivatives being introduced as CFC-replacements can be transformed to TFA (trifluoroacetate) in the atmosphere. Moreover, TFA is extremely stable in the environment, and this has raised questions regarding how widespread TFA is in the environment. We found that TFA is ubiquitous in precipitation: samples of rain from Ireland and Poland and snow from Canada, Sweden, New Zealand, and East Antarctica contained 1-1100 ng/L, and, studying a firn core drilled in Antarctica, concentrations of 3-56 ng/L were measured in layers formed during the 19th century. We have confirmed the preindustrial presence of significant background concentrations of trifluoroacetate in historic precipitation samples from the analysis of firn. Extensive procedures were enforced to prevent sample contamination.

Natural Background Levels of Trifluoroacetate in Rain and Snow

A firn core was drilled in Dronning Maud Land, Antarctica, to investigate the presence of haloacetates in snow that had accumulated over the past 200 years. By employing GC-MS detection of methyl esters of haloacetic acids, we were able to measure haloacetate concentrations down to one or a few nanograms per liter. Trichloroacetate (TCA) and dibromoacetate (DBA) were found in firn at concentrations that clearly exceeded the blank level of the applied analytical procedure, with mean concentrations estimated to 12 and 6 ng/L, respectively. There were also indications that mono- and dichloroacetate (MCA and DCA) were present in firn, whereas monobromoacetate (MBA) was found only in samples of surficial snow. We concluded that there is a significant natural background level of TCA and DBA in precipitation based on the following: (i) several of samples represented snow accumulated in the 19th century, (ii) haloacetates can be expected to be immobile in Antarctic firn, (iii) extensive measures were taken to prevent sample contamination, and (iv) blank levels of the analytical procedure used were low and stable. In addition, our results suggested that MCA and DCA also occur naturally in precipitation.

Annika T. Nielsen

Papers

Hydrogen production from organic waste

Quantification of volatile sulfur compounds in complex gaseous matrices by solid-phase microextraction.

Trace determination of volatile sulfur compounds by solid-phase microextraction and GC-MS

Natural Background Levels of Trifluoroacetate in Rain and Snow

Chloro- and Bromoacetates in Natural Archives of Firn from Antarctica