Characterization of biochars and dissolved organic matter phases obtained upon hydrothermal carbonization of Elodea nuttallii.

The invasive aquatic plant Elodea nuttallii was subjected to hydrothermal carbonization at 200 °C and 240 °C to produce biochar. About 58% w/w of the organic carbon of the pristine plant was translocated into the solid biochar irrespectively of the operating temperature. The process water rich in dissolved organic matter proved a good substrate for biogas production. The E. nuttallii plants showed a high capability of incorporating metals into the biomass. This large inorganic fraction which was mainly transferred into the biochar (except sodium and potassium) may hamper the prospective application of biochar as soil amendment. The high ash content in biochar (∼ 40% w/w) along with its relatively low content of organic carbon (∼ 36% w/w) is associated with low higher heating values. Fatty acids were completely hydrolyzed from lipids due to hydrothermal treatment. Low molecular-weight carboxylic acids (acetic and lactic acid), phenols and phenolic acids turned out major organic breakdown products.

Organic breakdown products resulting from hydrothermal carbonization of brewer's spent grain.

Hydrothermal carbonization of brewer's spent grain resulted in a solid hydrochar and an aqueous phase rich in macromolecular dissolved organic matter. Both phases were analyzed with regard to low molecular weight organic compounds (MW<500 Da) in lyophilized form by exhaustive solvent extraction followed by pre-chromatographic derivatization and GC/MS-analysis. Low molecular weight acids, O-functionalized phenols, cyclopentenone derivatives, and benzenediols accounted for the majority of organic analytes in both hydrothermal carbonization product streams while being absent in solvent extracts of the pristine biomass. The pattern of short chain functionalized acids in the pristine biomass and in the hydrothermally produced matrices turned out very different. Acylglycerines as the most abundant lipids in pristine brewer's spent grain were quantitatively hydrolyzed under hydrothermal conditions. The recovery of total fatty acids present in the pristine biomass amounted to 19%. The major fraction of hydrophobic breakdown products including fatty acids, fatty alcohols, and sterols was sorbed onto the hydrochar.

Hydrothermal carbonization of poly(vinyl chloride).

Poly(vinyl chloride) (PVC) was subjected to hydrothermal carbonization in subcritical water at 180-260 °C. Dehydrochlorination increased with increasing reaction temperature. The release of chlorine was almost quantitative above ∼235 °C. The fraction of organic carbon (OC) recovered in the hydrochar decreased with increasing operating temperature from 93% at 180 °C to 75% at 250 °C. A wide array of polycyclic aromatic hydrocarbons (PAHs) could be detected in the aqueous phase, but their combined concentration amounted to only ∼140 µg g(-1) PVC-substrate at 240 °C. A pathway for the formation of cyclic hydrocarbons and O-functionalized organics was proposed. Chlorinated hydrocarbons including chlorophenols could only be identified at trace levels (low ppb). Polychlorinated dibenzodioxins (PCDDs) and dibenzofurans (PCDFs) could not be detected. The sorption potential of the hydrochar turned out to be very low, in particular for polar organic pollutants. Our results provide strong evidence that hydrothermal carbonization of household organic wastes which can be tied to co-discarded PVC-plastic residues is environmentally sound regarding the formation of toxic organic products. Following these findings, hydrothermal treatment of PVC-waste beyond operating temperatures of ∼235 °C to allow complete release of organic chlorine should be further pursued.

Identification of oxidative coupling products of xylenols arising from laboratory-scale phytoremediation.

Oxidative coupling reactions take place during the passage of xylenols through a laboratory-scale helophyte-based constructed wetland system. Typical coupling product groups including tetramethyl-[1,1'-biphenyl] diols and tetramethyl diphenylether monools as stable organic intermediates could be identified by a combination of pre-chromatographic derivatization and GC/MS analysis. Structural assignment of individual analytes was performed by an increment system developed by Zenkevich to pre-calculate retention sequences. The most abundant analyte turned out to be 3,3',5,5'-tetramethyl-[1,1'-biphenyl]-4,4'-diol, which can be formed by a combination of radicals based on 2,6-xylenol or by an attack of a 2,6-xylenol-based radical on 2,6-xylenol. Organic intermediates originating from oxidative coupling could also be identified in anaerobic constructed wetland systems. This finding suggested the presence of (at least partly) oxic conditions in the rhizosphere.

Characterization of biocoals and dissolved organic matter phases obtained upon hydrothermal carbonization of brewer's spent grain.

The wet biomass brewer's spent grain was subjected to hydrothermal carbonization to produce biocoal. Mass balance considerations indicate for about two thirds of the organic carbon of the input biomass to be transferred into the biocoal. The van Krevelen plot refers to a high degree of defunctionalization with decarboxylation prevailing over dehydration. Calorific data revealed a significant energy densification of biocoals as compared to the input substrate. Sorption coefficients of organic analytes covering a wide range of hydrophobicities and polarities on biocoal were similar to those for dissolved humic acids. Data from GC/MS analysis indicated that phenols and benzenediols along with fatty acids released from bound lipids during the hydrothermal process constituted abundant products. Our findings demonstrate that the brewer's spent grain by-product is a good feedstock for hydrothermal carbonization to produce biocoal, the latter offering good prospects for energetic and soil-improving application fields.

Structural characterization of organic intermediates arising from xylenol degradation by laboratory-scale constructed wetlands.

A mixture of xylenols (2,6-, 3,4-, 3,5-) was subjected to laboratory-scale constructed wetland treatment using helophytes. Conversion efficiencies under aerobic conditions ranged from 89% to 94%; the corresponding numbers under anaerobic conditions were lower. The studies were focused on the identification of stable organic intermediates. Identification was performed by a combination of GC/MS analysis and pre-chromatographic derivatization of the lyophilizates. In addition to common intermediates including citraconate, succinate and dimethyl benzenediols, an array of α- and ß-ketoadipic acid carboxylates could be identified. The ketoadipic acid carboxylates have not been known to be formed in bioremediation of phenols including xylenols so far. Mechanisms for the formation of ketoadipic acid carboxylates are proposed. Chemotaxonomic considerations using diagnostic fatty acids provided mounting evidence that organic matter originating from plants prevailed over bacterial organic matter. Biomarkers indicated a virtual absence of fungi and algae.

Organic compounds in olive mill wastewater and in solutions resulting from hydrothermal carbonization of the wastewater.

Organic components in olive mill wastewater (OMW) were analyzed by exhaustive solvent extraction of the lyophilisate followed by pre-chromatographic derivatization techniques and GC/MS-analysis of the extracts. Simple biophenols including tyrosol (Tyr), hydroxytyrosol (OH-Tyr) and homovanillic alcohol as well as complex biophenols including decarbomethoxy ligostride aglycon and decarbomethoxy oleuropein aglycon proved most abundant analytes. Hydroxylated benzoic and cinnamic acids are less abundant, which may indicate a humification process to have occurred. The pattern of organic components obtained from native OMW was compared with that obtained from hydrothermal carbonization (HTC) of the waste product. Former results provided strong evidence that HTC of OMW at 220°C for 14h results in an almost complete hydrolysis of complex aglycons. However, simple biophenols were not decomposed on hydrothermal treatment any further. Phenol and benzenediols as well as low molecular weight organic acids proved most abundant analytes which were generated due to HTC. Similarly to aglycons, lipids including most abundant acylglycerines and less abundant wax esters were subjected almost quantitatively to hydrolysis under hydrothermal conditions. Fatty acids (FAs) released from lipids were further decomposed. The pathways of volatile analytes in both native OMW and aqueous HTC solutions were studied by solventless headspace-Solid Phase Micro Extraction. Basically, a wide array low molecular alcohols and ketones occurring in native OMW survived the HTC process.

Hydrothermal carbonization of olive mill wastewater.

Hydrothermal carbonization (HTC) is an emerging technology to treat wet biomasses aimed at producing a biochar material. Herein, olive mill wastewater (OMW) was subjected to HTC. Mass balance considerations provide evidence that the yield of biochar is low (~30%, w/w), which is associated with a low fraction of carbohydrates in OMW. The combination of different preparation schemes, pre-chromatographic derivatization reactions and GC/MS analysis for the analysis of organic compounds in aqueous HTC-solutions allowed to identify and quantify a wide array of analytes which belong either to intrinsic constituents of OMW or to characteristic HTC-breakdown products. Biophenols, such as hydroxyl-tyrosol (OH-Tyr), tyrosol (Tyr) account for the most abundant members of the first group. Most abundant breakdown products include phenol and benzenediols as well as short-chain organic acids. Secoiridoids, such as decarbomethoxy ligostride aglycon and decarbomethoxy oleuropein aglycon, all of them being typical components of OMW, are less abundant in HTC-solutions.

Non-discriminating flash pyrolysis and thermochemolysis of heavily contaminated sediments from the Hamilton Harbor (Canada).

Analytical pyrolysis of sediments contaminated with pollutants of medium to high molecular weights (up to approximately 500 Da) is very challenging when using conventional pyrolysis systems due to discrimination of high molecular weight analytes. In the framework of this contribution, non-discriminating pyrolysis and thermochemolysis using rapid heating in a Silcosteel capillary were applied to study organic pollutants in heavily contaminated sediments taken from the Hamilton Harbor. The novel pyrolysis approach, requiring very small amounts of sample, turned out to be very useful as a rapid screening method, e.g. for risk assessment studies, proving superior to commonly used solvent extraction. Main pollutants in the sediments under study included aromatic hydrocarbons, chiefly originating from coal tar and petroleum. Polycyclic aromatic hydrocarbons (PAHs) beyond six-rings, including coronene and truxene, could be detected. Sequential tetramethyl ammonium hydroxide-induced thermochemolysis performed at 500 and 750 degrees C enabled the differentiation between organic pollutants sorbed onto the sediment matrix on the one hand, and structural moieties of the condensed polymeric humic sediment matrix along with bound residues on the other hand. Thermochemolysis at 500 degrees C removed sorbates quantitatively, leaving only bare polymeric humic matrix. Significant PAH source indicators provided evidence that the lipidic fraction sorbed onto the sediments originated from PAHs formed chiefly in coal combustion processes. The polymeric humic organic matter network of the less polluted sediment was mainly of petrogenic origin, whereas black carbon, kerogen, etc. contributed to the organic carbon of the heavily polluted sediment. Thermochemolysis at 500 degrees C was also used to study fatty acid profiles of the sediments. The fatty acid methyl ester patterns obtained for the two sites under study differed significantly, with strong indications that microbial attenuation of the pollutants at the heavily polluted site 2 was strongly suppressed.

New fractionation scheme for lipid classes based on "in-cell fractionation" using sequential pressurized liquid extraction.

A new preparation scheme is proposed to fractionate neutral lipids (acylglycerines, sterol esters, long-chain free fatty acids) from polar phospholipids in biological matrices. This fractionation is mandatory in the microbial community, for the control of bioremediation processes, in the study of phytoplankton growth in lakes and rivers, and in the quality control of processed food. Basically, a two-step pressurized liquid extraction (PLE) scheme is combined with an "in-cell-fractionation" using silica-based sorbents placed at the outlet of the PLE cartridge. The optimized extraction scheme consists of n-hexane/acetone (9:1, v/v) extraction at 50 degrees C (2 cycles, 10 min each) to obtain neutral lipids followed by chloroform/methanol (1:4, v/v) extraction at 110 degrees C (2 cycles, 10 min each). Thermally pre-treated silicic acid and cyanoproyl-modified silica turned out to be appropriate sorbents to ensure clear-cut boundaries between neutral lipids and phospholipids. The proposed protocol is superior to commonly used approaches consisting of an exhaustive lipid extraction followed by off-line lipid fractionation using solid-phase extraction (SPE) regarding fractionation efficiency, time and solvent consumption. In this paper, it is also shown that the transmethylation using trimethylchlorosilane/methanol (1:9, v/v) provides a complete reaction to give methyl esters without artefact formation across the array of different lipid classes even with polyunsaturated fatty acid moieties.

Sequential pressurized liquid extraction to determine brain-originating fatty acids in meat products as markers in bovine spongiform encephalopathy risk assessment studies.

A new approach using sequential pressurized liquid extraction described recently [J. Poerschmann, R. Carlson, J. Chromatogr. A, 1127 (2006) 18-25] was applied to determine lipid markers originating from central nervous system (CNS) tissue of cows in heat-processed sausages. These studies are very important in quality control as well as risk assessment studies in the face of the bovine spongiform encephalopathy (BSE) crisis. Diagnostic CNS lipid markers, which should not be present in meat products without CNS addition, were recognized on complete transesterification as polar 2-hydroxy-fatty acids (2OH-24:0, 2OH-24:1, 2OH-22:0, 2OH-18:0, shorthand designation) as well as odd-numbered non-branched fatty acids beyond C(22). An array of other fatty acids including lignoceric acid (24:0), nervonic acid (24:1), arachidonic acid (20:4), and polyunsaturated nC(22)-surrogates are strongly related to CNS lipids, but occur as traces in meat products without CNS addition as well, thus reducing their value as diagnostic markers. Samples including meat products without CNS addition, meat with 3% CNS addition, as well as pure CNS homogenates, were subjected to sequential PLE (pressurized liquid extraction) consisting of two steps: n-hexane/acetone 9:1 (v/v) extraction at 50 degrees C to remove neutral lipids, followed by chloroform/methanol 1:4 (v/v) extraction at 110 degrees C to isolate polar CNS lipids (two 10 min PLE cycles each). To enhance the fractionation efficiency, cyanopropyl modified silica as well as chemically not modified silica sorbent was used at the outlet of the PLE cartridge to retard polar lipids in the first extraction step. This method proved superior to widely distributed exhaustive lipid extraction followed by solid-phase extraction (SPE) using silica regarding lipid recoveries and clear-cut boundaries between lipid classes. Methodological studies showed that the alcoholysis using trimethylchlorosilane/methanol (1:9, v/v) is an excellent method for the complete transesterification of lipids and quantitative formation of methyl esters.

High heterotrophic bacterial production in acidic, iron-rich mining lakes.

The acidic mining lakes of Eastern Germany are characterized by their extremely low pH and high iron concentrations. Low concentrations of CO2 in the epilimnion due to the low pH and reduced light transmission due to dissolved ferric iron potentially limit phytoplankton primary production (PP), whereas dissolved organic carbon (DOC) may promote heterotrophic production of bacteria (HP). We, therefore, tested whether HP exceeds PP in three lakes differing in pH and iron concentration (mean pH 2.3-3.0, 23-500 mg Fe L(-1)). Bacterial biomass and HP achieved highest values in the most acidic, most iron-rich lake, whereas PP was highest in the least acidic lake. HP was often higher than PP (ratio HP/PP up to 11), indicating that planktonic PP was not the main carbon source for the bacteria. HP was not related to PP and DOC, but HP as well as bacterial biomass increased with decreasing pH. Light stimulated the formation of ferrous iron, changed the DOC composition, and increased the HP in laboratory experiments, suggesting that iron photoreduction caused DOC degradation. This may explain why we found the highest HP in the most acidic and most rich lake. Overall, the importance of bacteria in the cycling of matter and as a basis for the whole food web seemed to increase in more acidic lakes with higher iron concentrations.

Fatty acid patterns in Chlamydomonas sp. as a marker for nutritional regimes and temperature under extremely acidic conditions.

Fatty acid profiles were used to characterize nutritional pathways in Chlamydomonas sp. isolated from an acidic mining lake (pH 2.7). Surprisingly, profiles of Chlamydomonas sp. grown in the lab under photoautotrophic, mixotrophic, and heterotrophic conditions at in situ deep strata lake water temperatures (8 degrees C) were very similar, polyunsaturated fatty acids including alpha-linolenic acid (18:3omega3) and 16:4omega3 along with palmitic acid (16:0) being most abundant. Therefore, heterotrophic growth of Chlamydomonas sp. at low temperatures can result in high concentrations of polyunsaturated fatty acids, as previously only described for some psychrophilic bacteria. By contrast, the cultivation of isolated Chlamydomonas sp. at 20 degrees C, reflecting surface water temperatures, provided fatty acid patterns characteristic of the nutrition strategy applied: the concentration of polyunsaturated fatty acids decreased when the growth pathway changed from photoautotrophic via mixotrophic to heterotrophic. Total fatty acid concentration also diminished in this order. Principal component analysis confirmed the significance of FA profiling to mirror nutritional pathways. Lake-water analysis revealed low concentrations of dissolved organic carbon, mainly consisting of polymeric fulvic acids that are unable to support heterotrophic growth of Chlamydomonas sp. Polymeric fulvic acids present in the deeper strata of the lake turned out to be formed in situ on the basis of organic monomers including reduced sulfur-containing ones, as revealed by thermochemolysis and pyrolysis. Growth of Chlamydomonas sp. in the deep chlorophyll maximum is therefore assumed to mainly result from photosynthesis, despite very low photon densities. Phytol-including metabolites proved to be significant biomarkers to indicate the nutritional pathway of Chlamydomonas sp. alpha, omega-Dicarboxylic acids-light-induced degradation products of unsaturated fatty acids-appeared to be good indicators of photooxidative alterations to the algal species under study.

In-column pyrolysis: a new approach to an old problem.

High-molecular-weight fragments produced during pyrolysis of both natural and synthetic materials often carry the most significant structural information. Their diagnostic value is usually limited when using commercial pyrolysis devices because of analyte discrimination on transfer from the pyrolysis unit to the GC column. A device enabling pyrolysis in line with GC column was developed to overcome this problem. Pyrolysis is carried out in a segment of deactivated stainless steel tubing. One end of the tubing is connected through a restrictor to a standard GC injector, and the other end is connected to a precolumn followed by a GC column. Pyrolysis is carried out by passing a pulse of electric current from a capacitive discharge power supply through the tubing. Nondiscriminated alkane pattern up to C-58 (limited by the temperature limit of the GC stationary phase) was observed for the pyrolysis of polyethylene. A comparison of conventional pyrolysis with in-column pyrolysis indicates that the range of semivolatile pyrolysis products that can be detected in the pyrograms extends much further toward higher-boiling compounds for the technique proposed. The new approach has also proved very useful in methodical variations of pyrolysis, including thermochemolysis using tetramethylammonium hydroxide.

Sorption of very hydrophobic organic compounds (VHOCs) on dissolved humic organic matter (DOM). 2. Measurement of sorption and application of a Flory-Huggins concept to interpret the data.

Sorption phenomena of very hydrophobic compounds (VHOCs, log K(OW) > 5) on dissolved humic organic matter (DOM) are overwhelmingly based on partitioning processes. In this respect, DOM is very similar to "rubbery" soil/sediment OM. To exclude system adsorption effects, the DOM sorption coefficients (K(DOM)) of VHOCs were determined using a dynamic approach based on the VHOCs' aqueous solubility enhancement in the presence of DOM. Partition coefficients are strongly correlated to the analytes' Kow across the alkane, PAH, and PCB groups under study. These three "families" are regarded to be good models of hydrophobic partitioning. On the basis of a uniform one-parameter concept characterizing sorption on amorphous polymers, Hildebrand solubility parameters of amorphous polymeric sorbents, including DOM, and of sorbates can be calculated on the basis of partition coefficients. Likewise, partition coefficients can be estimated using Hildebrand solubility parameters. Literature-based partition coefficients on DOM fit very well in this universal one-parameter concept. On using our own sorption data of PAHs, PCBs, and alkanes on DOM, an almost identical solubility parameter for the DOM polymer under study is obtained. The concept is also very useful in understanding both waterborne and airborne bioconcentration processes, which are considered to be partitioning phenomena.