Patrick Louchouarn

Comparison of quantification methods to measure fire‐derived (black/elemental) carbon in soils and sediments using reference materials from soil, water, sediment and the atmosphere

Black carbon (BC), the product of incomplete combustion of fossil fuels and biomass (called elemental carbon (EC) in atmospheric sciences), was quantified in 12 different materials by 17 laboratories from different disciplines, using seven different methods. The materials were divided into three classes: (1) potentially interfering materials, (2) laboratory-produced BC-rich materials, and (3) BC-containing environmental matrices (from soil, water, sediment, and atmosphere). This is the first comprehensive intercomparison of this type (multimethod, multilab, and multisample), focusing mainly on methods used for soil and sediment BC studies. Results for the potentially interfering materials (which by definition contained no fire-derived organic carbon) highlighted situations where individual methods may overestimate BC concentrations. Results for the BC-rich materials (one soot and two chars) showed that some of the methods identified most of the carbon in all three materials as BC, whereas other methods identified only soot carbon as BC. The different methods also gave widely different BC contents for the environmental matrices. However, these variations could be understood in the light of the findings for the other two groups of materials, i.e., that some methods incorrectly identify non-BC carbon as BC, and that the detection efficiency of each technique varies across the BC continuum. We found that atmospheric BC quantification methods are not ideal for soil and sediment studies as in their methodology these incorporate the definition of BC as light-absorbing material irrespective of its origin, leading to biases when applied to terrestrial and sedimentary materials. This study shows that any attempt to merge data generated via different methods must consider the different, operationally defined analytical windows of the BC continuum detected by each technique, as well as the limitations and potential biases of each technique. A major goal of this ring trial was to provide a basis on which to choose between the different BC quantification methods in soil and sediment studies. In this paper we summarize the advantages and disadvantages of each method. In future studies, we strongly recommend the evaluation of all methods analyzing for BC in soils and sediments against the set of BC reference materials analyzed here.

Terrigenous dissolved organic matter in the Arctic Ocean and its transport to surface and deep waters of the North Atlantic

isotopic compositions of DOM are depleted in 13 Cb y 1–2% relative to those in the Atlantic and Pacific. The large contribution of terrigenous DOM from Arctic rivers is responsible for the elevated concentrations of DOC in polar surface waters. The distribution of terrigenous DOM in polar surface waters is very heterogeneous, but on average we estimate 14–24% of the DOC is of terrestrial origin. Stable nitrogen isotopic compositions were useful for distinguishing DOM of Pacific and Atlantic origins as well as terrigenous and marine origins. The size distribution and composition of lignin phenols provide some evidence of photochemical transformations of terrigenous DOM, but it appears this process is not extensive in polar surface waters. The extent to which terrigenous DOM is removed from the Arctic Ocean by microbial degradation is less clear and warrants further study. Physical transport of terrigenous DOC to the North Atlantic is a major mechanism for its removal from the Arctic. The East Greenland Current alone exports 4.4–6.6 Tg of terrigenous DOC annually to the North Atlantic. Terrigenous DOC of Arctic origin was identified for the first time in components of North Atlantic Deep Water. Preliminary estimates indicate that � 1 Tg of terrigenous DOC is exported from the Arctic in Denmark Strait Overflow Water with an additional � 0.7 Tg in Classical Labrador Sea Water. Together, these exports compose approximately 25–33% of the terrigenous DOC discharged annually to the Arctic via rivers.

An index-based approach to assessing recalcitrance and soil carbon sequestration potential of engineered black carbons (biochars).

The ability of engineered black carbons (or biochars) to resist abiotic and, or biotic degradation (herein referred to as recalcitrance) is crucial to their successful deployment as a soil carbon sequestration strategy. A new recalcitrance index, the R(50), for assessing biochar quality for carbon sequestration is proposed. The R(50) is based on the relative thermal stability of a given biochar to that of graphite and was developed and evaluated with a variety of biochars (n = 59), and soot-like black carbons. Comparison of R(50), with biochar physicochemical properties and biochar-C mineralization revealed the existence of a quantifiable relationship between R(50) and biochar recalcitrance. As presented here, the R(50) is immediately applicable to pre-land application screening of biochars into Class A (R(50) ≥ 0.70), Class B (0.50 ≤ R(50) < 0.70) or Class C (R(50) < 0.50) recalcitrance/carbon sequestration classes. Class A and Class C biochars would have carbon sequestration potential comparable to soot/graphite and uncharred plant biomass, respectively, whereas Class B biochars would have intermediate carbon sequestration potential. We believe that the coupling of the R(50), to an index-based degradation, and an economic model could provide a suitable framework in which to comprehensively assess soil carbon sequestration in biochars.

Historical and geographical variations of sources and transport of terrigenous organic matter within a large-scale coastal environment

Abstract Elemental and molecular analyses indicate that the sources and inputs of terrigenous organic matter (OM) to the upper St. Lawrence system have been influenced by increased discharges of industrial solid organic wastes from the pulp and paper industry following its expansion in the 1920–1940s. Moderately altered lignin-rich particles from a combination of natural and anthropogenic sources predominate within recent sediments of this system, with anthropogenic fractions ranging 10–70% and 2–30% for the Fjord and the Lower Estuary, respectively. Compositional and isotopic signatures of sedimentary OM show that the sediments within the Lower Estuary are dominated by inputs of allochthonous OM (60–80%), whereas terrigenous OM inputs are minor (15–30%) sources of OM to the Gulf/Shelf sediments. In this latter environment, the terrigenous OM pool is composed exclusively of highly altered lignin-poor soil OM with no substantial influence from anthropogenic lignin. A global mass balance calculation suggests that about half of the global annual riverine flux is degraded, leaving only the remaining half to accumulate predominantly (98%) within shelf and slope sediments. This estimate suggests that lignin does not behave conservatively within the marine environment but supports some sort of organic matter degradation.

Sources and early diagenesis of lignin and bulk organic matter in the sediments of the Lower St. Lawrence Estuary and the Saguenay Fjord

Elemental and molecular organic matter concentrations were analyzed in sediments from the Lower St. Lawrence Estuary and the Saguenay Fjord in order to evaluate the historic evolution of pulp and paper mills solid-waste inputs in the system in the last decades and the relative reactivities of lignin and bulk organic materials in coastal sediments. A qualitative estimation of vascular plant sources to the Saguenay Fjord shows that the sedimentary terrigenous plant material is comprised predominantly of gymnosperm woods. In the deeper sediment horizons of the upper Saguenay basin, low intensive lignin parameters (C/V and S/V) and high percentages of lignin to total sedimentary organic carbon ( > 20%) all indicate elevated concentrations of woody gymnosperm tissues unprecedented in coastal sediments and directly related to the intense activity of the regions pulp and paper industries. The increased control on solid organic wastes from industrial effluents into the Saguenay river in the late 1980s to early 1990s is clearly apparent from increasing intensive parameter values and decreasing lignin fractions to the total sedimentary organic carbon (= 6-8%) in the upper basin surface sediments. Elemental and molecular analyses of fjord sediments, all indicate that most of the solid-phase discharge of lignified material by the pulp and paper industry is deposited rapidly close to the mouth of the river without reaching the downstream basins. In the St. Lawrence Estuary, intensive lignin parameters indicate that gymnosperm tissues are a major component of the sedimentary vascular plant material but with a significant fraction composed of angiosperm and nonwoody tissues. These latter types of organic tissues are particularly important components of terrigenous material in sediments deposited prior to the 1910-1920s. Acid/aldehyde ratios in most cores studied do not indicate clear-cut oxidative degradation of lignin material prior to its introduction in the aquatic system. The only exceptions are the two estuarine cores, where slightly elevated acid/aldehyde ratios relative to the range for fresh vascular plant tissues, might indicate mild aerobic fungal degradation of the sedimentary lignin material. Organic carbon, total nitrogen, organic phosphorus and lignin derived phenols all exhibited decreasing concentrations with core depth in the sediments of the Lower St. Lawrence Estuary. First-order degradation rate constants for all four chemical categories ranged between 0.02-0.05 yr -1 . The order of apparent reactivity among the different organic compounds is TN ≥ C org > P org > lignin at the head of the Laurentian channel and lignin TN = C org > P org further downstream. The surprising diagenetic selectivity observed at the upstream station is probably due to a higher flux of fresh, labile organic matter that reaches the sediment-water interface and degrades preferentially to more refractory materials such as lignin. Further downstream, little diagenetic selectivity was observed below the sediment-water interface indicating an overall refractory nature of the sedimentary organic matter. Finally, the differences in reactivity observed between C org and P org at both stations contradict earlier assumptions that no fractionation occurs between organic carbon and phosphorus during anaerobic degradation.

Generalized Two-Dimensional Perturbation Correlation Infrared Spectroscopy reveals Mechanisms for the Development of Surface Charge and Recalcitrance in Plant-derived Biochars

Fundamental knowledge of how biochars develop surface-charge and resistance to environmental degradation is crucial to their production for customized applications or understanding their functions in the environment. Two-dimensional perturbation-based correlation infrared spectroscopy (2D-PCIS) was used to study the biochar formation process in three taxonomically different plant biomass, under oxygen-limited conditions along a heat-treatment-temperature gradient (HTT; 200-650 °C). Results from 2D-PCIS pointed to the systematic, HTT-induced defragmenting of lignocellulose H-bonding network and demethylenation/demethylation, oxidation, or dehydroxylation/dehydrogenation of lignocellulose fragments as the primary reactions controlling biochar properties along the HTT gradient. The cleavage of OH(...)O-type H-bonds, oxidation of free primary hydroxyls to carboxyls (carboxylation; HTT ≤ 500 °C), and their subsequent dehydrogenation/dehydroxylation (HTT > 500 °C) controlled surface charge on the biochars; while the dehydrogenation of methylene groups, which yielded increasingly condensed structures (R-CH(2)-R →R═CH-R →R═C═R), controlled biochar recalcitrance. Variations in biochar properties across plant biomass type were attributable to taxa-specific transformations. For example, apparent inefficiencies in the cleavage of wood-specific H-bonds, and their subsequent oxidation to carboxyls, lead to lower surface charge in wood biochars (compared to grass biochars). Both nontaxa and taxa-specific transformations highlighted by 2D-PCIS could have significant implications for biochar functioning in fire-impacted or biochar-amended systems.

EARLY DIAGENETIC PROCESSES IN RECENT SEDIMENTS OF THE GULF OF ST-LAWRENCE:PHOSPHORUS, CARBON AND IRON BURIAL RATES

Abstract Selective extraction procedures were used to quantify different forms of solid-phase phosphorus, carbon and iron in marine sediments, and to evaluate the impact of authigenic formation of mineral forms such as carbonate fluorapatite (CFA), calcium carbonate (CaCO3) and pyrite (FeS2) on major elemental cycles during early diagenesis. Detrital P and Fe phases were successfully used as indicators of the constancy or variability of detrital inputs to several sedimentary environments from the deep channels of the Gulf of St-Lawrence. In cores characterized by near steady state influx rates, solid-phase P, C and Fe data and sediment burial rates indicate that CFA, CaCO3 and probably FeS2 are currently forming in the sediments of the Gulf. However, high concentrations and/or formation of CaCO3 in marine sediments appear to inhibit the formation of authigenic CFA. On the other hand, the formation of FeS2 does not influence authigenic CFA precipitation. In the deep troughs of the Gulf of St-Lawrence, total P burial rates range from ≈ 50 to 500 mgP/m2/yr. Truly authigenic precipitation of CFA, when observed, may represent up to ≈ 25% of the total burial rate of P. Bioturbation of sub-surface sediments reduces the potential for authigenic precipitation of CFA and CaCO3, thus affecting immobilization reactions that have a strong impact on the global oceanic cycles of C and P. The spatial heterogeneity of diagenetic reactions precludes the establishment of an accurate quantification of P removal on the scale of a continental shelf such as the Gulf of St-Lawrence.

Influence of combustion conditions on yields of solvent-extractable anhydrosugars and lignin phenols in chars: Implications for characterizations of biomass combustion residues

Anhydrosugars, such as levoglucosan and its isomers (mannosan, galactosan), as well as the solvent-extractable lignin phenols (methoxylated phenols) are thermal degradation products of cellulose/hemicellulose and lignin, respectively. These two groups of biomarkers are often used as unique tracers of combusted biomass inputs in diverse environmental media. However, detailed characterization of the relative proportion and signatures of these compounds in highly heterogeneous plant-derived chars are still scarce. Here we conducted a systematic study to investigate the yields of solvent-extractable anhydrosugars and lignin phenols in 25 lab-made chars produced from different plant materials under different combustion conditions. Solvent-extractable anhydrosugars and lignin phenols were only observed in chars formed below 350°C and yields were variable across different combustion temperatures. The yields of mannosan (M) and galactosan (G) decreased more rapidly than those of levoglucosan (L) under increasing combustion severity (temperature and duration), resulting in variable L/M and L/(M+G) ratios, two diagnostic ratios often used for identification of combustion sources (e.g. hardwoods vs. softwoods vs. grasses). Our observations thus may provide an explanation for the wide ranges of values reported in the literature for these two ratios. On the other hand, the results of this study suggest that the ratios of the major solvent-extractable lignin phenols (vanillyls (V), syringyls (S), cinnamyls (C)) provide additional source reconstruction potential despite observed variations with combustion temperature. We thus propose using a property-property plot (L/M vs. S/V) as an improved means for source characterization of biomass combustion residues. The L/M-S/V plot has shown to be effective in environmental samples (soil organic matter, atmospheric aerosols) receiving substantial inputs of biomass combustion residues.

The contribution of mangrove expansion to salt marsh loss on the Texas Gulf Coast.

Landscape-level shifts in plant species distribution and abundance can fundamentally change the ecology of an ecosystem. Such shifts are occurring within mangrove-marsh ecotones, where over the last few decades, relatively mild winters have led to mangrove expansion into areas previously occupied by salt marsh plants. On the Texas (USA) coast of the western Gulf of Mexico, most cases of mangrove expansion have been documented within specific bays or watersheds. Based on this body of relatively small-scale work and broader global patterns of mangrove expansion, we hypothesized that there has been a recent regional-level displacement of salt marshes by mangroves. We classified Landsat-5 Thematic Mapper images using artificial neural networks to quantify black mangrove (Avicennia germinans) expansion and salt marsh (Spartina alterniflora and other grass and forb species) loss over 20 years across the entire Texas coast. Between 1990 and 2010, mangrove area grew by 16.1 km2, a 74% increase. Concurrently, salt marsh area decreased by 77.8 km2, a 24% net loss. Only 6% of that loss was attributable to mangrove expansion; most salt marsh was lost due to conversion to tidal flats or water, likely a result of relative sea level rise. Our research confirmed that mangroves are expanding and, in some instances, displacing salt marshes at certain locations. However, this shift is not widespread when analyzed at a larger, regional level. Rather, local, relative sea level rise was indirectly implicated as another important driver causing regional-level salt marsh loss. Climate change is expected to accelerate both sea level rise and mangrove expansion; these mechanisms are likely to interact synergistically and contribute to salt marsh loss.

Combustion-derived substances in deep basins of Puget Sound: historical inputs from fossil fuel and biomass combustion.

Reconstructions of 250 years historical inputs of two distinct types of black carbon (soot/graphitic black carbon (GBC) and char-BC) were conducted on sediment cores from two basins of the Puget Sound, WA. Signatures of polycyclic aromatic hydrocarbons (PAHs) were also used to support the historical reconstructions of BC to this system. Down-core maxima in GBC and combustion-derived PAHs occurred in the 1940s in the cores from the Puget Sound Main Basin, whereas in Hood Canal such peak was observed in the 1970s, showing basin-specific differences in inputs of combustion byproducts. This system showed relatively higher inputs from softwood combustion than the northeastern U.S. The historical variations in char-BC concentrations were consistent with shifts in climate indices, suggesting an influence of climate oscillations on wildfire events. Environmental loading of combustion byproducts thus appears as a complex function of urbanization, fuel usage, combustion technology, environmental policies, and climate conditions.