Sources of sedimentary humic substances: vascular plant debris

A modern Washington continental shelf sediment was fractionated densimetrically using either an organic solvent, CBrCl₃, or aqueous ZnCl₂. The resulting low density materials (<2.06 g/ml) account for only 1% of the sediment mass but contain 25% of the sedimentary organic carbon and 53% of the lignin. The C/N ratios (30–40) and lignin phenol yields ($\text{Λ = 8}$) and compositions indicate that the low density materials are essentially pure vascular plant debris which is slightly enriched in woody (versus nonwoody) tissues compared to the bulk sediment. The low density materials yield approximately one-third of their organic carbon as humic substances and contribute 23% and 14% of the total sedimentary humic and fulvic acids, respectively. Assuming that the lignin remaining in the sedimentary fraction is also contained in plant fragments that yield similar levels of humic substances, then 50% and 30% of the total humic and fulvic acids, respectively, arise directly from plant debris.Base-extraction of fresh and naturally degraded vascular plant materials reveals that significant levels of humic and fulvic acids are obtained using classical extraction techniques. Approximately 1–2% of the carbon from fresh woods and 10–25% from leaves and bark were isolated as humic acids and 2–4 times those levels as fulvic acids. A highly degraded hardwood yielded up to 44% of its carbon as humic and fulvic acids. The humic acids from fresh plants are generally enriched in lignin components relative to carbohydrates and recognizable biochemicals account for up to 50% of the total carbon. Humic and fulvic acids extracted directly from sedimentary plant debris could be responsible for a major fraction of the biochemical component of humic substances.     

Effects of humus on the environmental activity of mineral-bound Hg: Influence on Hg volatility

The effects of three humus fractions (fulvic acid, brown humic acid and grey humic acid) on the volatility of five types of mineral-bound Hg were investigated. Fulvic acid was found to strongly promote the volatilization of Hg bound by Fe₂O₃, MnO₂ and kaolinite, but suppressed the volatilization of Hg bound by bentonite and CaCO₃. Brown humic acid was found to enhance the volatilization of Hg bound from all the tested minerals, except for Fe₂O₃. Grey humic acid had the weakest effect in promoting or suppressing Hg volatilization. The influence of the various humus fractions on the volatilization of mineral-bound Hg is closely related to the complexing capacity and complex stability of the particular humus material. The higher the complexing capacity and the lower the complex stability, the more prominent is the humus material in promoting Hg volatility. The Hg sorption capacity and sorption strength of the minerals, as well as their Hg speciation characteristics, limit the effect that humus has to volatilize Hg.     

Comparison of the Complexation of Cu and Cd by Humic or Fulvic Acids and by Ligands Observed in Lake Waters

The complexation of Cu and Cd by ligands observed in filtered unfractionated lakewaters is compared to the complexation by humic and fulvic acids. Complexation parameters (conditional stability constants and ligand concentrations) of Suwannee River fulvic acids (FA), purified peat humic acids (HA) and of ligands in lakewater samples have been determined using the same methods (ligand-exchange and CSV (cathodic stripping voltammetry) or ASV (anodic stripping voltammetry)), and the same titration ranges of Cu, Cd and organic carbon concentrations. The performance of the used techniques is first evaluated in FA and HA suspensions, and gives comparable results with the literature values for the same materials, according to published models (5-site model, NICA model) and parameters. Model calculations using the WHAM model for FA and HA (Tipping, 1994) are also presented. The comparison of titrations of FA and HA with Cu and Cd with those of lakewater samples indicates that stronger ligands than FA and HA are present at low concentrations in the lakewaters. Specific strong ligands occur in particular in eutrophic lake waters, whereas in a lake with higher metal concentrations and low biological productivity the ligands more closely match the fulvic acid characteristics.     

Influence of natural organic acids on the Mg/Ca ratio in the bottom sediments of highly mineralized lakes

Thermodynamic modeling of equilibria in the system water–rock–organic acids was used to study the influence of organic acids on Ca and Mg redistribution between a solution and a solid phase in connection with the use of calcites of variable composition Ca_xMg_1–xCO₃ as indicators of paleoclimatic environments. In the thermodynamic model, high-molecular humic substances (fulvic + humic acids) were represented by a set of independent metal-binding centers. Therefore, their number was preset based on the given density of proton- or metal-binding sites. The numerical implementation of several geochemical situations involving the dissolution/deposition of calcites with different Mg contents showed that the main effect of fulvic and humic acids is the acidification of solutions and the reduction of carbonate stability. Although humic substances can play an important role in fixing Ca and Mg and removing them from solution, their actual concentrations in natural media (<<1 g/L) do not cause significant changes in the composition of Ca_xMg_1–xCO₃ phases. On the other hand, there is quantitative evidence that variations in the Mg/Ca ratio in a solution and a solid phase are significantly influenced by the evaporative concentration of Mg-oversaturated solutions, alkalization/acidification during their evolution, or CO₂ content variations owing to changes in climate and lake activity.     

Analytical problems in determining peptide nitrogen in the humic fractions of three Italian soils

Peptides were released from organic matter fractions of three Italian soils (humin, humic and fulvic acids), when the samples were hydrolyzed in Ba(ON)₂-saturated solution at 105°C for 2 hr. The peptides obtained were separated using electrophoresis and paper chromatography. The presence of polypeptides in the soil organic matter was indicated by: (1) their hydrolysis by pronase; (2) the amino acids released by 6 N HCl hydrolysis; (3) The comparison of i.r. spectra of humic fractions before and after hydrolysis with 6 N HCl.Attempts at isolating the native proteinaceous compounds using electrophoresis in polyacrylamide gel failed; additionally, our attempts to hydrolyze proteinaceous components enzymatically in unfractionated soil organic matter, as well as in its fractions, before and after methylation, with pepsin, papain and pronase, were unsuccessful. Pronase demonstrated a weak proteolytic activity only at very low substrate-enzyme ratios (20 : 1) in humic and fulvic fractions and in whole phyrophosphate extract. Deproteinated substrates treated with pronase also released free amino acids, suggesting autodigestion.In humin, humic and fulvic fractions we found a total amino acid content of 40–45%, 12–24% or 1–85, respectively. Amino acid recovery from single fractions was about 70–80% of the total content in the unfractionated soil.     

Proton-binding study of standard and reference fulvic acids, humic acids, and natural organic matter

The acid-base properties of 14 standard and reference materials from the International Humic Substances Society (IHSS) were investigated by potentiometric titration. Titrations were conducted in 0.1 M NaCl under a nitrogen atmosphere, averaging 30 min from start to finish. Concentrations of carboxyl groups and phenolic groups were estimated directly from titration curves. Titration data were also fit to a modified Henderson-Hasselbalch model for two classes of proton-binding sites to obtain “best fit” parameters that describe proton-binding curves for the samples. The model was chosen for its simplicity, its ease of implementation in computer spreadsheets, and its excellent ability to describe the shapes of the titration curves. The carboxyl contents of the IHSS samples are in the general order: terrestrial fulvic acids > aquatic fulvic acids > Suwannee River natural organic matter (NOM) > aquatic humic acids > terrestrial humic acids. Overall, fulvic acids and humic acids have similar phenolic contents; however, all of the aquatically derived samples have higher phenolic contents than the terrestrially derived samples. The acid-base properties of reference Suwannee River NOM are surprisingly similar to those of standard Suwannee River humic acid. Results from titrations in this study were compared with other published results from both direct and indirect titrations. Typically, carboxyl contents for the IHSS samples were in agreement with the results from both methods of titration. Phenolic contents for the IHSS samples were comparable to those determined by direct titrations, but were significantly less than estimates of phenolic content that were based on indirect titrations with Ba(OH)₂ and Ca(OAc)₂. The average phenolic-to-carboxylic ratio of the IHSS samples is approximately 1:4. Models that assume a 1:2 ratio of phenolic-to-carboxylic groups may overestimate the relative contribution of phenolic groups to the acid-base chemistry of humic substances.     

The distribution and nature of amino acids and other nitrogen-containing compounds in Lake Ontario surface sediments

Five surface sediment samples (0–3 cm), two suspended sediment samples and a zooplankton sample from Lake Ontario were analysed for nitrogen-containing compounds. Amino acids, amino sugars, ethanolamine and urea were separated and characterized by ion-exchange chromatography. Free amino acids and soluble combined amino acids and amino sugars accounted for less than 0–25 per cent of the total nitrogen in the sediments. Insoluble combined amino acids and amino sugars were the most abundant nitrogen fraction in the sediments, making up from 49 to 55 per cent of the total nitrogen. Evidence is presented that asparagine, glutamine and citrulline are present in the interstitial waters and may make up part of the sediment organic nitrogen that was not characterized.The free amino acids released by the proteolytic enzyme, pronase, from the interstitial waters and sediment humic and fulvic acid extracts were determined. Pronase released 65 per cent of the soluble combined amino acids and 34 per cent of the fulvic acid amino acids as free amino acids. Enzyme activity was inhibited in the presence of the humic acid extract. The results indicate that the combined amino acids in the interstitial waters and fulvic acid extracts are intermediates between the primary aquatic detritus and the sediment humic acids. The enzyme experiments and infra-red data indicate that part of the sediment amino acids are combined through peptide linkages.     

N-15 NMR spectra of naturally abundant nitrogen in soil and aquatic natural organic matter samples of the International Humic Substances Society

The naturally abundant nitrogen in soil and aquatic NOM samples from the International Humic Substances Society has been characterized by solid state CP/MAS ¹⁵N NMR. Soil samples include humic and fulvic acids from the Elliot soil, Minnesota Waskish peat and Florida Pahokee peat, as well as the Summit Hill soil humic acid and the Leonardite humic acid. Aquatic samples include Suwannee River humic, fulvic and reverse osmosis isolates, Nordic humic and fulvic acids and Pony Lake fulvic acid. Additionally, Nordic and Suwannee River XAD-4 acids and Suwannee River hydrophobic neutral fractions were analyzed. Similar to literature reports, amide/aminoquinone nitrogens comprised the major peaks in the solid state spectra of the soil humic and fulvic acids, along with heterocyclic and amino sugar/terminal amino acid nitrogens. Spectra of aquatic samples, including the XAD-4 acids, contain resolved heterocyclic nitrogen peaks in addition to the amide nitrogens. The spectrum of the nitrogen enriched, microbially derived Pony Lake, Antarctica fulvic acid, appeared to contain resonances in the region of pyrazine, imine and/or pyridine nitrogens, which have not been observed previously in soil or aquatic humic substances by ¹⁵N NMR. Liquid state ¹⁵N NMR experiments were also recorded on the Elliot soil humic acid and Pony Lake fulvic acid, both to examine the feasibility of the techniques, and to determine whether improvements in resolution over the solid state could be realized. For both samples, polarization transfer (DEPT) and indirect detection (¹H–¹⁵N gHSQC) spectra revealed greater resolution among nitrogens directly bonded to protons. The amide/aminoquinone nitrogens could also be observed by direct detection experiments.     

Gaseous mercury emissions from urban surfaces: Controls and spatiotemporal trends

The spatial and temporal variability of Hg emissions from urban paved surfaces was assessed through repeated measurements under varying environmental conditions at six sample sites in Toronto, Ontario, Canada. The results show significant spatial variability of the Hg emissions with median values ranging from below detection limit to 5.2 ng/m²/h. Two of the sites consistently had higher Hg emissions (on several occasions >20 ng/m²/h) than the other 4, which were equivalently low (maximum emission: 2.1 ng/m²/h). A surrogate measure of the pavement Hg concentrations was obtained during each day of sampling through the collection of street dust. The median street dust concentration also showed significant spatial variability (ranging from 9.6 to 44.5 ng/g). Regression analysis showed that the spatial variability of the Hg emissions was significantly related to the street dust concentrations. Controlled experiments using Hg amended street dust confirmed the relationship between Hg surface concentration and emission magnitude. Within a given sample site, Hg emissions varied temporally and multiple regression analysis showed that within-site variability was significantly influenced by changes in solar radiation with only a minor effect from surface temperature. Controlled experiments using shade cloths confirmed that solar radiation can have a large influence on the magnitude of Hg emissions within a given site. The emissions measured in Toronto were contextualized through comparison sampling in Austin, Texas. The Hg emissions measured in Austin were within the range detected in Toronto and also showed significant correlation with Hg street dust concentrations between sites. To provide a holistic assessment of Hg emissions from urban environments, samples were also collected from other common urban surfaces (soil, roofs, and windows). Soils consistently had higher emissions than all the other surfaces (7.3 ng/m²/h, n = 39).     

Relationships between heavy metals and iron oxides,fulvic acids,particle size fractions in urban roadside soils

Urban roadside soils are the “recipients” of large amounts of heavy metals from a variety of sources including vehicle emissions, coal burning waste and other activities. The behavior of heavy metals in urban roadside soils depends on the occurrence as well as the total amount. Accordingly, knowledge of the interactions between heavy metals and other constituents in the soil is required to judge their environmental impact. In this study, correlations of heavy metal concentrations (Pb, Zn, Cu, Ag, Se, Ni, Cr and Ba) to iron extracted using dithionite–citrate–bicarbonate (DCB) buffer (Fe_DCB), fulvic acids and particle size fractions were examined from the Xuzhou urban roadside soils. Heavy metals except for Cr and fulvic acids had a positive significant correlation with Fe_DCB, indicating these metals and fulvic acids are principally associated with the surfaces of iron oxides of the soils. Significant positive correlations were also found between the contents of fulvic acids and heavy metals, showing these heavy metals (especially for Cu, Ni and Cr) form stable complexes with fulvic acids. Such finding is of importance with regard to the increased mobilization of heavy metals, e.g., into freshwater ecosystems. Ag, Se and Cr are independent of particle size fractions because of their low concentrations of Ag and Se in the studied soils. Pb, Zn, Cu, Ba and Ag are mainly enriched in the finer soil particles (especially <16 μm).     

Effect of fulvic acids on sorption of U(VI), Zn,Yb, I and Se(IV) onto oxides of aluminum,iron and silicon

The sorption of Yb³⁺, UO²⁺₂, Zn²⁺, I⁻ and SeO²⁻₃ onto Al₂O₃, Fe₂O₃ and SiO₂ were determined by a batch technique in the presence and absence of fulvic acids. The effects of fulvic acid on sorption were compared. The existing general consensus, that humic substances tend to enhance metal cation sorption at low pH, reduce metal cation sorption at high pH and reduce inorganic anion sorption between pH values 3 to 10, was generally shown to be true. However, in this work many exceptions to the general consensus were found. The study indicated that the effect of humic substances on sorption of inorganic cations or anions depends not only on pH, but also on the nature of the oxide, the nature of humic substance, fractionation of the humic substance by sorption, the relative strength of complexes of both soluble and sorbed humic substances, the extent of surface coverage by humic substance, the initial concentration of humic substance and the inorganic electrolyte composition.     

Methylation patterns of aquatic humic substances determined by13C NMR spectroscopy

¹³C NMR spectroscopy is used to examine the hydroxyl group functionality of a series of humic and fulvic acids from different aquatic environments. Samples first are methylated with¹³C-labeled diazomethane. The NMR spectra of the diazomethylated samples allow one to distinguish between methyl esters of car☐ylic acids, methyl ethers of phenolic hydroxyls, and methyl ethers of phenolic hydroxyls adjacent to two substituents. Samples are then permethylated with¹³C-labeled methyl iodide/NaH.¹³C NMR spectra of permethylated samples show that a significant fraction of the hydroxyl groups is not methylated with diazomethane alone. In these spectra methyl ethers of carbohydrate and aliphatic hydroxyls overlap with methyl ethers of phenolic hydroxyls. Side reactions of the methyltion procedure including carbon methylation in the CH₃I/NaH procedure, are also examined. Humic and fulvic acids from bog, swamp, groundwater, and lake waters showssome differences in their distribution of hydroxyl groups, mainly in the concentrations of phenolic hydroxyls, which may be attributed to their different biogeochemical origins.     

Ultrafiltration of fulvic and humic acids,a comparison of stirred cell and hollow fiber techniques

The ultrafiltration of solutions of well characterized samples of fulvic and humic acids or their salts, using two different techniques, show that these materials are retained by commercial ultrafiltration membranes with molecular weight cut-off values far higher than the reported molecular weights of fulvic or humic acid. The lower molecular weight fulvic acid or its Na⁺ -salt is retained even better than the higher molecular weight Na⁺-salt of humic acid. Both stirred cell and hollow fiber techniques can be employed to concentrate or desalt solutions of these humic materials, with relatively small solute losses. Very high simple electrolyte backgrounds (above 1 M) lower the performance of a given membrane considerably, moderate concentrations of simple electrolyte do not influence the ultrafiltration efficiency.     

Total mercury and methylmercury in sediments near offshore drilling sites in the Gulf of Mexico

Concentrations of total Hg in sediments near six drilling sites in the Gulf of Mexico were elevated well above average background values of 40–80 ng/g. The excess Hg was associated with barite from discharged drilling mud. In contrast with total Hg, concentrations of methylmercury (MeHg) in these sediments did not vary significantly at nearfield (<100 m) versus farfield (>3 km) distances from the drilling sites. Observed variability in concentrations of MeHg were related to local differences in redox state in the top 10 cm of sediment. Low to non-detectable concentrations of MeHg were found in nearfield sediments that were anoxic, highly reducing and contained abundant H₂S. At most drilling sites, nearfield samples with high concentrations of total Hg (>200 ng/g) had similar or lower amounts of MeHg than found at background (farfield) stations. Higher values of MeHg were found in a few nearfield sediments at one site where concentrations of TOC were higher and where sediments were anoxic and moderately reducing. Overall, results from this study support the conclusion that elevated concentrations of MeHg in sediments around drilling sites are not a common phenomenon in the Gulf of Mexico.     

Effects of age on the chemical structure of paleosol humic acids and fulvic acids

Humic acids and fulvic acids were extracted from six paleosols in Southern Italy. Humic acids (HAs) constituted between 96.5 and 99.2% of the total extracts; the remaining materials consisted of fulvic acids (FAs). Radiocarbon ages of the HAs ranged from about 6,000 to close to 29,000 years B.P., δ¹³C values averaged $\text{?25.6 ± 0.3‰}$ The HAs were characterized by chemical (elemental and functional group analyses) and spectroscopic (IR, ESR, ¹³CNMR, E₄/E₆ ratios) methods. FAs were characterized by chemical methods, E₄/E₆ ratios and IR spectra.The chemical and spectroscopic analyses showed practically no differences in the chemical structure and composition of the six HAs and FAs, so that age appeared to have little effect on these parameters. The paleosols were found to be closed systems with low polysaccharide and protein contents, thus providing unfavorable substrates for microbial activity. The preservation of the humic materials in the paleosols may have been due to low biological activity and/or to retention by amorphous minerals. The HAs did not appear to be affected by temperatures higher than 170–200°C over the 23,000 year period which we observed.     

Distribution of As,Cr, Ni,Rb, Ti and Zr between peat and its humic fraction along an undisturbed ombrotrophic bog profile (NW Switzerland)

Ombrotrophic bogs are useful records of the impact of historical human activity on heavy metal contamination. Several studies concerning the trace element record (mainly Pb and Hg) in these particular environments have been carried out in recent years, although the role of humic substances has often not been considered. In particular, of the components of peat organic matter, fulvic acids and low molecular weight compounds are generally responsible for the mobility of trace elements through the profile, while humic acids (HAs) are involved in the formation of more stable organo-mineral complexes. In order to study the parallel distribution of As, Cr, Ni, Rb, Ti and Zr in bulk peat and the corresponding HAs, a peat core (10 × 10 × 81 cm) was collected from Etang de la Gruère (Switzerland) and cut into 27 slices of 3 cm. The samples were freeze-dried and milled very finely, and HAs extracted from each sample. Both peat and HAs were analyzed using an energy-dispersive miniprobe X-ray fluorescence multielement analyser (EMMA-XRF). Of the considered elements, Ni showed a great affinity for the humic acid component, while Cr was concentrated mainly into humic material from the deeper layers. On the other hand, Ti, Zr and Rb seemed to reflect the variation in mineral material both in peat and HA samples, while the As content of both materials reflected the environmental conditions characterizing the bog.     

Mercury in the Southern Ocean

We present here the first mercury speciation study in the water column of the Southern Ocean, using a high-resolution south-to-north section (27 stations from 65.50°S to 44.00°S) with up to 15 depths (0-4440 m) between Antarctica and Tasmania (Australia) along the 140°E meridian. In addition, in order to explore the role of sea ice in Hg cycling, a study of mercury speciation in the “snow-sea ice-seawater” continuum was conducted at a coastal site, near the Australian Casey station (66.40°S; 101.14°E). In the open ocean waters, total Hg (Hg_T) concentrations varied from 0.63 to 2.76 pmol L⁻¹ with “transient-type” vertical profiles and a latitudinal distribution suggesting an atmospheric mercury source south of the Southern Polar Front (SPF) and a surface removal north of the Subantartic Front (SAF). Slightly higher mean Hg_T concentrations (1.35 ± 0.39 pmol L⁻¹) were measured in Antarctic Bottom Water (AABW) compared to Antarctic Intermediate water (AAIW) (1.15 ± 0.22 pmol L⁻¹). Labile Hg (Hg_R) concentrations varied from 0.01 to 2.28 pmol L⁻¹, with a distribution showing that the Hg_T enrichment south of the SPF consisted mainly of Hg_R (67 ± 23%), whereas, in contrast, the percentage was half that in surface waters north of PFZ (33 ± 23%). Methylated mercury species (MeHg_T) concentrations ranged from 0.02 to 0.86 pmol L⁻¹. All vertical MeHg_T profiles exhibited roughly the same pattern, with low concentrations observed in the surface layer and increasing concentrations with depth up to an intermediate depth maximum. As for Hg_T, low mean MeHg_T concentrations were associated with AAIW, and higher ones with AABW. The maximum of MeHg_T concentration at each station was systematically observed within the oxygen minimum zone, with a statistically significant MeHg_Tvs Apparent Oxygen Utilization (AOU) relationship (p < 0.001). The proportion of Hg_T as methylated species was lower than 5% in the surface waters, around 50% in deep waters below 1000 m, reaching a maximum of 78% south of the SPF. At Casey coastal station Hg_T and Hg_R concentrations found in the “snow-sea ice-seawater” continuum were one order of magnitude higher than those measured in open ocean waters. The distribution of Hg_T there suggests an atmospheric Hg deposition with snow and a fractionation process during sea ice formation, which excludes Hg from the ice with a parallel Hg enrichment of brine, probably concurring with the Hg enrichment of AABW observed in the open ocean waters. Contrastingly, MeHg_T concentrations in the sea ice environment were in the same range as in the open ocean waters, remaining below 0.45 pmol L⁻¹. The MeHg_T vertical profile through the continuum suggests different sources, including atmosphere, seawater and methylation in basal ice. Whereas Hg_T concentrations in the water samples collected between the Antarctic continent and Tasmania are comparable to recent measurements made in the other parts of the World Ocean (e.g., Soerensen et al., 2010), the Hg species distribution suggests distinct features in the Southern Ocean Hg cycle: (i) a net atmospheric Hg deposition on surface water near the ice edge, (ii) the Hg enrichment in brine during sea ice formation, and (iii) a net methylation of Hg south of the SPF.     

Variability in dissolved organic matter fluorescence and reduced sulfur concentration in coastal marine and estuarine environments

Fluorescence characterization of dissolved organic matter (DOM) and measurements of Cr-reducible sulfide (CRS) are presented for 72 coastal marine and estuarine water samples obtained from the USA and Canada. Each sample is identified according to source: terrigenous, autochthonous, wastewater or mixed. Fluorescence data are resolved into contributions from humic, fulvic, tyrosine and tryptophan-like fluorophores. Humic and fulvic-like fluorophores correlate well with dissolved organic C (DOC) (r² = 0.73 and 0.71, respectively) but tyrosine and tryptophan-like fluorophores show no correlation with DOC. Quality factors are identified by normalization of fluorescence contributions to DOC. Humic and fulvic components show no statistical differences between sources but the amino acid-like fluorescence quality factors show significant variations between source, with highest values for autochthonous sources (0.07 ± 0.01 arbitrary fluorescence units per mg of C) versus low values (0.015 ± 0.005) for terrigenous source waters. CRS concentrations are highly variable from 0.07 ± 0.01 to 7703 ± 98 nM and do no correlate with DOC except when terrigenous source waters (n = 13) are separated out from the total sample set (r² = 0.55). There is an open question in the literature; does DOC source matter in terms of protective effects towards metal toxicity? Here is shown that DOC molecular-level quality does vary and that this variation is mostly in terms of the contributions of amino acids to total fluorescence.     

Sensitivity of the global atmospheric cycle of mercury to emissions

A systematic investigation of the impact of current uncertainties in Hg emissions from specific source categories on global air Hg concentrations is presented. First, the uncertainties in different emission source categories are discussed and then the results of a base simulation and three sensitivity simulations conducted with a global chemical transport model for mercury (CTM-Hg) are presented. The total Hg emissions in the four scenarios range from 6600 to 9400 Mg/a. The sensitivity studies investigate the impact of the range in uncertainty in natural emissions, emissions of previously deposited Hg, and anthropogenic emissions both in China and worldwide, while taking into account constraints imposed by available data (current/pre-industrial emission ratio of 2–4). In one case, natural emissions and emissions of previously deposited Hg were changed to represent a mid point of the range of values found in the literature. This lead to a 16% increase in background emissions, i.e., natural emissions and emissions of previously deposited Hg combined. Increasing natural emissions by 16% or Chinese anthropogenic emissions by 100% yielded atmospheric Hg concentrations comparable with those measured across the globe without any changes to the atmospheric chemistry. Increasing natural emissions and emissions of previously deposited Hg by 16% and all anthropogenic emissions by 100% as compared to the base scenario yielded atmospheric Hg concentrations that were not compatible with measurements and changes in the chemical behavior of Hg in the atmosphere would be required to yield results that are consistent with observed Hg concentrations. The current uncertainty in total Hg emissions at the global scale is placed at about a factor of two.     

Pyrolysis-mass spectrometry/pattern recognition on a well-characterized suite of humic samples

A suite of well-characterized humic and fulvic acids of freshwater, soil and plant origin was subjected to pyrolysis-mass spectrometry and the resulting data were analyzed by pattern recognition and factor analysis. A factor analysis plot of the data shows that the humic acids and fulvic acids can be segregated into two distinct classes. Carbohydrate and phenolic components are more pronounced in the pyrolysis products of the fulvic acids, and saturated and unsaturated hydrocarbons contribute more to the humic acid pyrolysis products. A second factor analysis plot shows a separation which appears to be based primarily on whether the samples are of aquatic or soil origin.