Adsorption Characteristics and the Effect of Dissolved Organic Matter on Mercury(II) Adsorption of Various Soils in China

To evaluate the adsorption characteristics and effects of dissolved organic matter (DOM) from wheat straw (DOM_W) and swine manure (DOM_S) on mercury [Hg(II)] adsorption by soils, a series of experiments was conducted on 26 soils with different soil properties.Results showed that the values of K_d (a solid–liquid partition coefficient) of soils varied within a range of 0.768–14.386 L g^?1. K_d values were mainly controlled by soil organic matter (SOM), cation exchange capacity (CEC), soil nitrogen (N), and soil sulfur (S). When DOM_W and DOM_S were added to the soil samples, the amount of Hg(II) adsorbed by the soils decreased significantly. Furthermore, based on the decreased percentage of adsorption of Hg(II) by soil upon adding DOM_W (P_DOMW) or DOM_S (P_DOMS), about 73.08% soils, the values of P_DOMS were smaller than those of P_DOMW. The P_DOMW values were related to SOM, pH, free Fe oxide content, and CEC, whereas P_DOMS values were related to soil free Fe/Al oxide contents. Therefore, we should pay more attention about mercury risk caused by the addition of exogenous organic matter in soils, especially for the soils with low or high pH, less SOM, low CEC, and less free Fe/Al oxide.     

Effects of dissolved organic matter from sewage sludge on the atrazine sorption by soils

The effects of dissolved organic matter (DOM), water soluble organic matter derived from sewage sludge, on the sorption of atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-trazine) by soils were studied using a batch equilibrium technique. Six paddy soils, chosen so as to have different organic carbon contents, were experimented in this investigation. Atrazine sorption isotherms on soils were described by the linear equation, and the distribution coefficients without DOM (K_d) or with DOM (K_d ^*) were obtained. Generally, the values of K_d ^*/K_d initially increased and decreased thereafter with increasing DOM concentrations of 0–60 mg DOC · L^?1 in soil-solution system form. Critical concentrations of DOM (DOM_np) were obtained where the value of K_d ^* was equal to K_d. The presence of DOM with concentrations lower than DOM_np promoted atrazine sorption on soils (K_d ^* > K_d), whereas the presence of DOM with concentrations higher than DOM_np tended to inhibit atrazine sorption (K_d ^* < K_d). Interestingly, DOM_np for tested soils was negatively correlated to the soil organic carbon content, and the maximum of K_d ^*/K_d (i.e.K _max) correlated positively with the maximum of DOM sorption on soil (X_max). Further investigations showed that the presence of hydrophobic fraction of DOM evidently promoted the atrazine sorption on soils, whereas the presence of hydrophilic DOM fraction obviously tended to inhibit the atrazine sorption. Interactions of soil surfaces with DOM and its fractions were suggested to be the major processes determining atrazine sorption on soils. The results of this work provide a reference to the agricultural use of organic amendment such as sewage sludge for improving the availability of atrazine in soils.     

Influence of the Interactions Between Black Carbon and Soil Constituents on the Sorption of Pyrene

Biochar (a kind of black carbon (BC)) has been advocated as a promising additive to farmland, thus it is crucial to understand the influence of BC on the fate of hydrophobic organic chemicals (HOCs) when they exist in soil. This study explored the sorption of pyrene onto a BC sample obtained by pyrolyzing pine sawdust, two soils, clay (kaolinite), and the mixtures thereof to investigate the influence of the interactions between BC and soil constituents on the sorption of HOCs and the mechanisms therein. Sorption of pyrene onto soil?BC mixtures was significantly less than that predicted by the sum of the individual soil and BC sorption, indicating that the sorption of pyrene onto soil and BC did not occur independently. The reduction of BC sorption capacity in soil seemed primarily to be caused by soil dissolved organic matter (DOM), which attenuated pyrene sorption onto BC by 18.7%?40.3% (within pyrene equilibrium concentration range of 0.05?0.5 S _w). These were likely due to the blockage of micropores, reduced accessibility of sorption sites, and binding of pyrene by DOM in aqueous solution. In addition to the DOM effect, kaolinite also diminished pyrene sorption onto BC to some extent, which suggested additional interaction between BC and soil particles. Pyrene sorption onto the soil?BC mixtures varied with water content and contact time. The influence of wet versus dry conditions and contact time on the K_oc of pyrene was more obvious when pyrene equilibrium concentrations were lower. The effect of aging also varied with soil properties. In summary, BC could not behave independently in soil, and its sorption capacity was changed by its interactions with soil constituents, which may be influenced by soil properties, environmental condition, and contact time.     

Sorption of dissolved organic matter by mineral soils of the Siberian forest tundra

Because of low net production in arctic and subarctic surface water, dissolved organic matter (DOM) discharged from terrestrial settings plays an important role for carbon and nitrogen dynamics in arctic aquatic systems. Sorption, typically controlling the export of DOM from soil, may be influenced by the permafrost regime. To confirm the potential sorptive control on the release of DOM from permafrost soils in central northern Siberia, we examined the sorption of DOM by mineral soils of Gelisols and Inceptisols with varying depth of the active layer. Water‐soluble organic matter in the O horizons of the Gelisols was less (338 and 407 mg C kg^?1) and comprised more dissolved organic carbon (DOC) in the hydrophobic fraction (HoDOC) (63% and 70%) than in the O horizons of the Inceptisols (686 and 706 mg C kg^?1, 45% and 48% HoDOC). All A and B horizons from Gelisols sorbed DOC strongly, with a preference for HoDOC. Almost all horizons of the Inceptisols showed a weaker sorption of DOC than those of the Gelisols. The C horizons of the Inceptisols, having a weak overall DOC sorption, sorbed C in the hydrophilic fraction (HiDOC) stronger than HoDOC. The reason for the poor overall sorption and also the preferential sorption of HiDOC is likely the high pH (pH>7.0) of the C horizons and the smaller concentrations of iron oxides. For all soils, the sorption of HoDOC related positively to oxalate‐ and dithionite–citrate‐extractable iron. The A horizons released large amounts of DOC with 46–80% of HiDOC. The released DOC was significantly (r=0.78, P<0.05) correlated with the contents of soil organic carbon. From these results, we assume that large concentrations of DOM comprising large shares of HiDOC can pass mineral soils where the active layer is thin (i.e. in Gelisols), and enter streams. Soils with deep active layer (i.e. Inceptisols), may release little DOM because of more frequent infiltration of DOM into their thick mineral horizons despite their smaller contents of reactive, poorly crystalline minerals. The results obtained for the Inceptisols are in agreement with the situation observed for streams connecting to Yenisei at lower latitudes than 65°50′ with continuous to discontinuous permafrost. The smaller sorption of DOM by the Gelisols is in agreement with the larger DOM concentrations in more northern catchments. However, the Gelisols preferentially retained the HoDOC which dominates the DOC in streams towards north. This discrepancy can be explained by additional seepage water from the organic horizons that is discharged into streams without intensive contact with the mineral soil.     

Sludge-Derived Cu and Zn in a Humic-Gley Soil: Effect of Dissolved Metal-Organic Matter Complexes on Sorption and Partitioning

A sequential extraction scheme was combined with sorption isotherm analysis in order to investigate sorption of sewage sludge-derived Cu and Zn to the A-horizon of a humic-gley soil as a whole, and to the operationally defined exchangeable (1?M MgCl₂), carbonate (1?M NaOAc), Fe/Mn oxide (0.04?M NH₂OH.HCl), and organic (0.02?M HNO₃+30% H₂O₂) soil fractions. Sorption parameters were compared for a sample of sludge leachate (with 97.4% of Cu and 63.2% of Zn present as dissolved metal-organic matter complexes, as calculated by geochemical modeling involving MINTEQA2 and verified using an ion exchange resin method) with that of a reference solution exhibiting the same chemical characteristics as the leachate, except for the presence of dissolved organic material. Dissolved metal-organic matter complexes were found to significantly (P<0.05) depress sorption to the bulk soil and each fraction. The greatest depression of Cu and Zn sorption was observed for the exchangeable, carbonate, and Fe/Mn oxide fractions, while the organic fraction of the soil was the least affected. This reflects a greater affinity for the exchangeable, carbonate, and Fe/Mn oxide fractions by the free divalent metal (Cu²⁺, Zn²⁺), with sorption by these fractions attributed to cation exchange, chemisorption, and co-precipitation processes. The sorption characteristics of the organic fraction indicated that Cu and Zn sorption by soil organic matter mostly involved dissolved metal-organic matter complexes. This may be attributed to hydrophobic interactions between nonpolar regions of the dissolved metal-organic matter complexes and solid-phase soil organic matter.     

Behavior and characteristics of DOM during a laboratory-scale horizontal subsurface flow wetland treatment: Effect of DOM derived from leaves and roots

In order to study the effect of dissolved organic matter (DOM) from the leaves and roots of wetland plants on the dissolved organic carbon (DOC) reduction during a laboratory-scale horizontal subsurface flow constructed wetland (HSFW) treatment, excitation–emission matrixces (EEMs) analysis was conducted as a tracer in an effort to understand the biological or physicochemical functioning of this complex environment. Using XAD-8/XAD-4 resins, the DOM in the secondary effluent, HSFW effluent, and the DOM derived from the leaves and roots (DOM_L&R) were fractionated into five classes: hydrophobic acid (HPO-A), hydrophobic neutral (HPO-N), transphilic acid (TPI-A), transphilic neutral (TPI-N) and hydrophilic fraction (HPI). DOC was removed by 37.2% during the HSFW treatment. On the other hand, hydrophobic/hydrophilic distribution of the HSFW effluent DOM changed significantly, with the effluent DOC becoming more hydrophobic due to a preferential removal of HPI (with a reduction of 64.8%). Furthermore, the trihalomethane formation potential (THMFP) reduction of the HSFW system was quite low (20.2%), partially being ascribed to the influence of the relatively higher specific THMFP (STHMFP) of the DOM_L&R fractions (especially for HPO-A). The soluble microbial by-products (SMPs) and aromatic protein-like materials (polyphenols) from the leaves and roots could be the main reason for the increased STHMFP of the HSFW effluent DOM fractions. In addition, the peak of Region II (λ_ex/λ_em = (220–260)/(332–380)) might serve as a proxy for monitoring the DOM_L&R (polyphenols) in the effluent from a matured wetland.     

Effects of dissolved organic matter from sewage sludge on the atrazine sorption by soils

The effects of dissolved organic matter (DOM), water soluble organic matter derived from sewage sludge, on the sorption of atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-trazine) by soils were studied using a batch equilibrium technique. Six paddy soils, chosen so as to have different organic carbon contents, were experimented in this investigation. Atrazine sorption isotherms on soils were described by the linear equation, and the distribution coefficients without DOM (Kd) or with DOM (Kd*) were obtained. Generally, the values of Kd*/Kd initially insoil-solution system form. Critical concentrations of DOM (DOMnp) were obtained where the value of Kd* was equal to Kd. The presence of DOM with concentrations lower than DOMnp promoted atrazine sorption on soils (Kd* ＞ Kd), whereas the presence of DOM with concentrations higher than DOMnp tended to inhibit atrazine sorption (Kd* ＜ Kd). Interestingly, DOMnp for tested soils was negatively correlated to the soil organic carbon content, and the maximum of Kd*/Kd (i.e.Kmax) correlated positively with the maximum of DOM sorption on soil (Xmax). Further investigations showed that the presence of hydrophobic fraction of DOM evidently promoted the atrazine sorption on soils, whereas the presence of hydrophilic DOM fraction obviously tended to inhibit the atrazine sorption. Interactions of soil surfaces with DOM and its fractions were suggested to be the major processes determining atrazine sorption on soils. The results of this work provide a reference to the agricultural use of organic amendment such as sewage sludge for improving the availability of atrazine in soils.     

Impact of Clay Minerals and DOM on the Competitive Sorption/Desorption of PAHs

Two model compounds were used to investigate sorptive phenomena of a silty-sand soil under single and binary solute systems at different concentrations. In the sorption isotherms, the presence of phenan-threne (PHE) exhibited a statistically significant (P<0.05) sorption competition over pyrene (PYR), regardless of the concentration. PYR influenced the PHE isotherms only when it was present at 15?mg/L. The concentration dependence in sorption competition was only evident for the more hy-drophobic PYR. In the presence of PHE, the fraction of desorbed PYR was significantly increased with an increase in PYR concentration. PHE desorption enhancement was the most observable with the higher initial concentration (15?mg/L). However, the presence of PYR did not affect PHE desorption. This study found that, based on equivalent solid mass, soils containing only clay minerals sorbed 12.2% more PHE than soils with only soil organic matter (SOM) for 3?mg/L PHE. Clay minerals also impacted desorption as evidenced by a 65% decrease in desorbed PYR fraction compared with when the soil only contained SOM. The dissolved organic matter (DOM) amendment did not increase desorption. Instead, PHE desorption was significantly inhibited by the added DOM. For this study, co-sorption was found to be the mechanism for the inhibited desorption.     

Copper Sorption Behavior of Selected Soils of the Oasis in the Middle Reaches of Heihe River Basin,China

The mobility and bioavailability of copper (Cu) depends on the Cu sorption capacity of soil and also on the chemical form of Cu in soils. Laboratory batch experiments were carried out to study the sorption and distribution of Cu in nine soils differing in their physicochemical properties from the oasis in the middle reaches of Heihe river basin, China: desert soil (S-1), agricultural soils (S-2, S-3, S-8, and S-9), marshland soil (S-4), and hungriness shrub soils (S-5 and S-6). Copper sorption behavior was studied using the sorption isotherm and sequential extraction procedure. In general, the sorption capacity for Cu decreased in the order: S-4 > S-9 > S-2 > S-8 > S-3 > S-6 > S-5 > S-7 > S-1. The correlation results suggest that soils with higher CEC, silt, clay, CaCO3, and organic matter will retain Cu more strongly and in greater amounts than soils that are sandy with lower CEC, CaCO3, and organic matter. pH is not an important impact factor to Cu sorption in experimental soil samples because pH in soils used in this study had a narrow range. The distribution of sorbed Cu varied between nine soils studied and depended on both soil properties and initial added Cu concentration. There are significant differences in the distribution of Cu in each soil with the increase of initial Cu concentration. The predominance of Cu associated with the available fraction, which was over 50% of the total sorbed Cu in most cases, indicates that the change of geochemical conditions might promote the release of Cu back into soil solution thus impacting organisms in the soils. The added Cu has also the tendencies to locate in the residual fraction, which was larger than 5% of the total amount extracted from the four fractions in most soils.     

Influence of Dissolved Organic Matter on Sorption and Desorption of 1,2,4-trichlorobenzene and 1,2,4,5-tetrachlorobenzene onto Wood Char

Sorption and desorption of 1, 2, 3-trichlorobenzene (TCB) and 1,2,4,5-tetrachlorobenzene (TeCB) onto wood char prepared from maple wood shavings heated at 500°C were studied in the presence of dissolved organic matter (DOM), including humic acid (HA), L-malic acid (L-MA), and peptone. Compared to TCB, TeCB exhibited more nonlinear and stronger sorption onto wood char. Nonlinearity of the sorption isotherms increased in the presence of DOM. The presence of HA enhanced the sorption capacity and desorption hysteresis of TCB and TeCB on wood char mainly due to the strong sorption of HA on wood char surface. Moreover, there were positive relations between K_d values of TCB and TeCB and the HA concentration (p < 0.01). In contrast, peptone reduced the sorption capacity and increased the sorption reversibility because of the partition of TCB and TeCB in peptone solution. L-MA at 50-200 mg·L^?1 also leads to a decrease in sorption capacity and irreversibility attributed to solubilization, although the sorbed L-MA on the wood char surface can slightly increase TCB and TeCB sorption. At the same concentration, peptone leads to a higher decrease in TCB sorption than L-MA. Also, negative correlations were found between K_d values of TCB and TeCB and the L-MA and peptone concentration (p < 0.01). Our results may help to understand the different impacts of DOM on the transport and fate of halogenated aromatic hydrocarbons in aquatic environments polluted with chars.     

Mercury (II) Adsorption on Three Contrasting Chinese Soils Treated with Two Sources of Dissolved Organic Matter: II. Spectroscopic Characterization

To reveal the influencing mechanism of dissolved organic matter (DOM) on mercury (Hg II) adsorption by black, red, and fluvo-aquic soils in China, Fourier transform infrared (FTIR) spectroscopy, ¹³C nuclear magnetic resonance (NMR) spectroscopy, and three-dimensional excitation emission matrix (3DEEM) fluorescence spectroscopy were employed to characterize the DOM samples and DOM-Hg complexes. FTIR spectra showed that the complexation of Hg (II) mainly acted on the C=O, COO^?, and O-H groups of DOM from swine manure (DOMs) and wheat straw (DOMw). The NMR spectra indicated that the complex reaction of Hg (II) and DOM corresponded with the change in carboxyl C. The NMR results also showed that the dominant C components in DOM were aromatic C, O-alkyl C, alkyl C, and carboxyl C, and that DOMw imposed more influence on Hg (II) adsorption than DOMs, which was consistent with that of FTIR spectroscopy. The 3DEEM showed that DOM contained both aromatic protein-like and fulvic-like substances, and that the protein-like properties of DOMs and UV fulvic-like fluorescence substances of DOMw can better participate in the formation of Hg complexes. This result provides strong direct evidence to elucidate the DOM-Hg (II) binding mechanism, and further interprets the effect mechanism of exogenous DOM on Hg adsorption by soil.     

Production of Total Potentially Soluble Organic C, N, and P Across an Ecosystem Chronosequence: Root versus Leaf Litter

Dissolved organic matter (DOM) plays several important roles in forest ecosystem development, undergoing chemical, physical and/or biological reactions that affect ecosystem nutrient retention. Very few studies have focused on gross rates of DOM production, and we know of no study that has directly measured DOM production from root litter. Our objectives were to quantify major sources of total potentially water-soluble organic matter (DOM_tps) production, with an emphasis on production from root litter, to quantify and compare total potentially soluble organic C, N, and P (DOC_tps, DON_tps, and DOP_tps) production, and to quantify changes in their production during forest primary succession and ecosystem development at the Mt. Shasta Mudflows ecosystem chronosequence. To do so, we exhaustively extracted freshly senesced root and leaf and other aboveground litter for DOC_tps, DON_tps, and DOP_tps by vegetation category, and we calculated DOM_tps production (g m⁻² y⁻¹) at the ecosystem level using data for annual production of fine root and aboveground litter. DOM production from throughfall was calculated by measuring throughfall volume and concentration over 2 years. Results showed that DOM_tps production from root litter was a very important source of DOM_tps in the Mount Shasta mudflow ecosystems, in some cases comparable to production from leaf litter for DON_tps and larger than production from leaf litter for DOP_tps. Total DOC_tps and DON_tps production from all sources increased early in succession from the 77- to the 255-year-old ecosystem. However, total DOP_tps production across the ecosystem chronosequence showed a unique pattern. Generally, the relative importance of root litter for total fine detrital DOC_tps and DON_tps production increased significantly during ecosystem development. Furthermore, DOC_tps and DON_tps production were predominantly driven by changes in biomass production during ecosystem development, whereas changes in litter solubility due to changes in species composition had a smaller effect. We suggest that DOM_tps production from root litter may be an important source of organic matter for the accumulation of SOM during forest ecosystem development. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users. Shauna M. Uselman, Robert G. Qualls, and Juliane Lilienfein conceived of or designed the study and performed research. SMU analyzed data and wrote the article. SMU and RGQ contributed new methods or models.     

Effect of Dissolved Organic Matter from Wheat Straw or Swine Manure on the Cu Adsorption in Three Chinese Soils

Batch equilibration experiments were conducted to evaluate the effects of dissolved organic matter (DOM) from wheat straw (DOMw) and swine manure (DOMs) on copper (Cu) adsorption and behavior in Haplic Phaeozems, Haplic Acrisol, and Eutric Fluvisol in China. Results showed that the Cu adsorption isotherms were well fitted with both Langmuir and Freundlich equations. The Cu maximum potential adsorption capacity of the three soils followed the order of Eutric Fluvisol > Haplic Phaeozems > Haplic Acrisol. DOMw and DOMs increased the Cu adsorption capacity in Haplic Phaeozems and Haplic Acrisol, and the promoting role of DOMs on Cu adsorption was obviously higher than that of DOMw. Increasing DOM concentration of DOMw and DOMs promoted the Cu adsorption in Haplic Phaeozems and Haplic Acrisol. However, this promoting effect weakened with increasing DOM concentration. Moreover, DOMw and DOMs inhibited the Cu adsorption in Eutric Fluvisol, and this inhibitory effect significantly increased with increasing DOM concentration. The results may be used to assess the potential environmental contamination of the studied soils and to control the application of organic fertilizers.     

Detrital Controls on Soil Solution N and Dissolved Organic Matter in Soils: A Field Experiment

We established a long-term field study in an old growth coniferous forest at the H.J. Andrews Experimental Forest, OR, USA, to address how detrital quality and quantity control soil organic matter accumulation and stabilization. The Detritus Input and Removal Treatments (DIRT) plots consist of treatments that double leaf litter, double woody debris inputs, exclude litter inputs, or remove root inputs via trenching. We measured changes in soil solution chemistry with depth, and conducted long-term incubations of bulk soils from different treatments in order to elucidate effects of detrital inputs on the relative amounts and lability of different soil C pools. In the field, the addition of woody debris increased dissolved organic carbon (DOC) concentrations in O-horizon leachate and at 30 cm, but not at 100 cm, compared to control plots, suggesting increased rates of DOC retention with added woody debris. DOC concentrations decreased through the soil profile in all plots to a greater degree than did dissolved organic nitrogen (DON), most likely due to preferential sorption of high C:N hydrophobic dissolved organic matter (DOM) in upper horizons; percent hydrophobic DOM decreased significantly with depth, and hydrophilic DOM had a much lower and less variable C:N ratio. Although laboratory extracts of different litter types showed differences in DOM chemistry, percent hydrophobic DOM did not differ among soil solutions from different detrital treatments in the field, suggesting that microbial processing of DOM leachate in the field consumed easily degradable components, thus equalizing leachate chemistry among treatments. Total dissolved N leaching from plots with intact roots was very low (0.17 g m⁻² year⁻¹), slightly less than measured deposition to this very unpolluted forest (~s 0.2 g m⁻² year⁻¹). Total dissolved N losses showed significant increases in the two treatments without roots whereas concentrations of DOC decreased. In these plots, N losses were less than half of estimated plant uptake, suggesting that other mechanisms, such as increased microbial immobilization of N, accounted for retention of N in deep soils. In long-term laboratory incubations, soils from plots that had both above- and below-ground litter inputs excluded for 5 years showed a trend towards lower DOC loss rates, but not lower respiration rates. Soils from plots with added wood had similar respiration and DOC loss rates as control soils, suggesting that the additional DOC sorption observed in the field in these soils was stabilized in the soil and not readily lost upon incubation.     

Variation in Phosphorus Sorption with Soil Particle Size

Phosphorus (P) is considered a primary cause for surface water eutrophication that leads to anoxia. Understanding the relationships between soil particle size and P sorption helps devise effective best management practices (BMPs) to control P transport by erosion, leaching, and overland flow from agricultural land. Consequently, this study examined the effect of surface soil particle size on the sorption of P in five soil series (four Ultisols and one Entisol) from the Mid-Atlantic region. The sorption of P in each soil was assessed by equilibrating (after shaking for 24?h) 5?g soil containing varied amounts of KH₂PO₄ in 20?mL of 0.01?M KCl solution. Phosphorus in solution was determined by the molybdate blue method of Murphy and Riley. The P adsorption characteristics of these soils were described using the Langmuir isotherm. Results indicated that variability in P sorption was related to particle size and soil type. Soil organic matter content contributed a great deal to P sorption in the Entisol. However, soil clay had influence on the P sorption characteristics of each soil. The maximum P retentive capacities of soils (as determined by Sm from Langmuir equation) and P sorbed at 500?mg P kg^?1 addition showed a linear relationship (r2 = 0.94). Therefore, based on the results obtained, the single point method of Bache and Williams may be appropriate to describe the maximum P sorption capacity of non-sandy soils, as observed in this study.     

Changes in dissolved lignin-derived phenols, neutral sugars, uronic acids, and amino sugars with depth in forested Haplic Arenosols and Rendzic Leptosols

A major part of the dissolved organic matter produced in the organic layers of forest ecosystems and leached into the mineral soil is retained by the upper subsoil horizons. The retention is selective and thus dissolved organic matter in the subsoils has different composition than dissolved organic matter leached from the forest floor. Here we report on changes in the composition of dissolved organic matter with soil depth based on C-to-N ratios, XAD-8 fractionation, wet-chemical analyses (lignin-derived CuO oxidation products, hydrolysable sugars and amino sugars) and liquid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy. Dissolved organic matter was sampled directly beneath the forest floor using tension-free lysimeters and at 90cm depth by suction cups in Haplic Arenosols under Scots pine (Pinus sylvestris L.) and Rendzic Leptosols under European beech (Fagus sylvatica L.) forest. At both sites, the concentrations of dissolved organic carbon (DOC) decreased but not as strongly as reported for deeply weathered soils. The decrease in DOC was accompanied by strong changes in the composition of dissolved organic matter. The proportion of the XAD-8-adsorbable (hydrophobic) fraction, carboxyl and aromatic C, and the concentrations of lignin-derived phenols decreased whereas the concentrations of sugars, amino sugars, and nitrogen remained either constant or increased. A general feature of the compositional changes within the tested compound classes was that the ratios of neutral to acidic compounds increased with depth. These results indicate that during the transport of dissolved organic matter through the soils, oxidatively degraded lignin-derived compounds were preferentially retained while potentially labile material high in nitrogen and carbohydrates tended to remain dissolved. Despite the studied soils' small capacity to sorb organic matter, the preferential retention of potentially refractory and acidic compounds suggests sorption by the mineral soil matrix rather than biodegradation to govern the retention of dissolved organic matter even in soils with a low sorption capacity.     

中亚热带森林转换对土壤可溶性有机质数量与光谱学特征的影响

选取中亚热带福建三明格氏栲天然林及其转换而成的木荷、锥栗及福建柏等3种人工林表层土壤(0—10 cm)可溶性有机质(DOM)为对象,对其数量和光谱学特征进行了研究,以探讨森林转换对土壤DOM的影响。结果表明,天然林转换成上述3种人工林后,0—5 cm土壤可溶性有机碳(DOC)浓度显著降低(P0.05),降低程度分别为66.1%,69.9%及29.4%,可溶性有机氮(DON)浓度也有所下降;除福建柏外,其余两种人工林5—10 cm土壤DOC及DON浓度均低于天然林。各林分0—5 cm土壤DOC及DON浓度均高于5—10 cm土层。两个土层中,天然林土壤DOM的芳香化及腐殖化程度均显著高于人工林(P0.05),但荧光效率值低于人工林;荧光光谱图显示,天然林土壤DOM在芳香性脂肪族及木质素类复杂结构荧光基团处的吸收大于人工林;各林分土壤DOM傅里叶红外光谱出现吸收谱带的位置相似,其中吸收强度最大的为形成氢键的—OH的伸缩振动,此外还有芳香性CC伸缩振动、有机羧酸盐COO-反对称伸缩振动、碳水化合物中烷氧基C—O的振动等,人工林土壤DOM中碳水化合物的比例增加是其结构简单的主要原因。土壤DOM中结构复杂、分子量大的组分不易向下迁移;天然林与人工林间土壤DOM数量及光谱学特征的差异主要与凋落物输入及营林措施的干扰有关;本研究所涉及的3种人工林中,福建柏更有利于土壤养分的累积。     

Compositional changes and molecular transformations of dissolved organic matter during the arctic spring floods in the lower Churchill watershed (Northern Manitoba,Canada)

The spring flood season in Northern aquatic systems is characterized by rapid changes in river discharge and fluxes of organic and inorganic species, yet remains under sampled. In this study, we examine the molecular characteristics and transformations of dissolved organic matter (DOM) during the Arctic spring season at three locations in the lower Churchill River watershed. Characteristics including dissolved organic carbon concentrations, optical properties (i.e. absorbance and, excitation-emission matrix fluorescence coupled with parallel factor analysis, EEM-PARAFAC) and molecular characterization using high resolution mass spectrometry (HR-MS) were assessed. As spring floods progressed, a significant reduction in DOM spectral slope (S_275–295) and an increase in absorbance (a₂₇₀) were observed suggesting an increase in DOM molecular weight and concentrations at all sampled locations. A maximum in HR-MS lignin-class compounds coincided with peak flow at all sampled locations, further validated with an increase in PARAFAC humic-like components and a minimum in S_275–295. Principal component analyses revealed that both protein and aromatic humic-like material measured by HR-MS and EEM-PARAFAC, respectively, were significantly correlated (ANOVA, p < 0.05), demonstrating similarities in both techniques. Based on network analysis of HR-MS assigned formula, the highest peak flow day was characterized by a maximum in homologous DOM of C₂H₂O and C₂H₄ additions, suggesting structural similarities in newly deposited lignin and humic material. Overall, the progression of the spring freshet shifted the lower Churchill River watershed from an environment rich in proteins and lipids to an aquatic system more abundant in lignin, aromatic and humic DOM.     

Fluorescence characteristics and biodegradability of dissolved organic matter in forest and wetland soils from coastal temperate watersheds in southeast Alaska

Understanding how the concentration and chemical quality of dissolved organic matter (DOM) varies in soils is critical because DOM influences an array of biological, chemical, and physical processes. We used PARAFAC modeling of excitation–emission fluorescence spectroscopy, specific UV absorbance (SUVA₂₅₄) and biodegradable dissolved organic carbon (BDOC) incubations to investigate the chemical quality of DOM in soil water collected from 25 cm piezometers in four different wetland and forest soils: bog, forested wetland, fen and upland forest. There were significant differences in soil solution concentrations of dissolved organic C, N, and P, DOC:DON ratios, SUVA₂₅₄ and BDOC among the four soil types. Throughout the sampling period, average DOC concentrations in the four soil types ranged from 9–32 mg C l⁻¹ and between 23–42% of the DOC was biodegradable. Seasonal patterns in dissolved nutrient concentrations and BDOC were observed in the three wetland types suggesting strong biotic controls over DOM concentrations in wetland soils. PARAFAC modeling of excitation–emission fluorescence spectroscopy showed that protein-like fluorescence was positively correlated (r ² = 0.82; P < 0.001) with BDOC for all soil types taken together. This finding indicates that PARAFAC modeling may substantially improve the ability to predict BDOC in natural environments. Coincident measurements of DOM concentrations, BDOC and PARAFAC modeling confirmed that the four soil types contain DOM with distinct chemical properties and have unique fluorescent fingerprints. DOM inputs to streams from the four soil types therefore have the potential to alter stream biogeochemical processes differently by influencing temporal patterns in stream heterotrophic productivity.