土壤腐殖物质特征及其对有机碳长时间尺度稳定性的指示：以陕西洛川黄土剖面为例

在长时间尺度上研究土壤中腐殖物质的组成和腐殖化特征对于正确评价土壤有机质的稳定性具有重要意义。文中对洛川黄土/古土壤剖面S8以上的17个黄土和古土壤样品中的胡敏酸（HA）、富里酸（FA）和胡敏素（HM）进行定量研究,并对HA和FA的E465、E665值等进行了测定。结合该课题组对矿物组成、总有机碳（TOC）及其各组分含...     

Rapid quantification of humic and fulvic acids by HPLC in natural waters

A simple method based on high-performance size-exclusion chromatography (HPSEC) has been developed for rapid quantification of humic and fulvic acids (HA and FA) in stream waters. A Tsk-gel column was used to separate natural dissolved organic matter (DOM) into two components: peak A and B. In terms of HPSEC chromatograms and fluorescence patterns, peak A and B were similar to the corresponding XAD-extracted HA and FA, respectively. It is suggested that peak A fraction mainly consisted of HA, and peak B fraction FA. The similar separation of HA and FA using HPSEC and a conventional XAD method suggests the consistency of molecular size distribution and physical–chemical properties of DOM. HPSEC offers a simple and rapid method for the quantification of HA and FA instead of tedious extractions of humic substances. Analyses of natural water samples show that the calculation of HA/FA based on UV absorbance was under- or over-estimated, the calibration using the extracted HS allows a more accurate quantification. The fast screening of HA and FA provides useful quantitative and qualitative information that can be used in environmental or monitoring studies.     

1H NMR spectra of humic and fulvic acids and their peracetic oxidation products

¹H NMR spectra of humic (HA) and fulvic (FA) acids and their oxidative degradation products are reported. The HA shows the presence of -(CH₂)_n - CH₃ (n > 6) chemical fragments belonging to n-alkanes and/or n-fatty acids physically adsorbed onto the macromolecule structure. These fragments are absent in the FA fraction. Both humic fractions reveal the presence of similar amounts of aromatic protons which partly undergo exchange phenomena. The importance of this experimental observation is discussed. Oxidative degradation seems to cause partial cleavage of aromatic rings, more pronounced in the FA than in the HA. The degraded FA shows a higher total acidity and a higher phenolic OH content than the degraded HA. Both degraded fractions display some sharp singlet signals at 1.9 and 3.9 ppm arising from protons belonging to repetitive chemical fragments probably formed during the oxidation reaction. Tentative assignments of these signals are given. A general analysis of the HA and FA degraded spectra seems to indicate that the chemical fragments which undergo peracetic oxidation are substantially similar. The extent of oxidation of the two humic fractions is different. The HA degradation products reveal the presence of oligomeric structures, whereas the degraded FA appears less resistant to the oxidizing agent.     

运用3DEEMs及荧光偏振方法研究pH、离子强度及浓度效应对腐殖酸荧光光谱特性的影响

利用三维荧光激发.发射光谱(3DEEMs)及荧光偏振法研究了3例腐殖酸和1例湖泊溶解有机物(DOM)在不同腐殖酸浓度、离子强度和pH条件下的荧光光谱特性.实验结果表明,随着浓度增大,各腐殖酸样的荧光强度增大,其中垃圾渗滤液腐殖酸和Pahokee泥炭腐殖酸的荧光峰出现红移.随着浓度进一步增大,腐殖酸的荧光偏振值增大,由此推断在此浓度范围内腐殖酸由于分子间的排斥作用使其构型出现伸展.离子强度增大导致腐殖酸及阿哈湖DOM的荧光强度降低.随着氯化钾(KCI)浓度增大,Fluka腐殖酸的荧光峰A蓝移,荧光峰B的荧光偏振值出现减小,推测是由于静电中和作用使其荧光基团发生卷曲造成的.离子强度对其余腐殖酸样和阿哈湖DOM的其他荧光特性没有明显的影响.总的来说,pH值的变化对腐殖酸和湖泊DOM的荧光特征的影响是很明显的.随着pH值增大,腐殖酸和湖泊DOM的荧光强度增强.而pH值减小时,Fluka腐殖酸和Pahokee泥炭腐殖酸的荧光峰(A峰)蓝移,当pH值降到5时,Fhka腐殖酸的荧光峰突然红移到最大,随后又继续蓝移;垃圾渗滤液腐殖酸和阿哈湖DOM的荧光峰位无明显的漂移.所有样品的荧光偏振值都减小(但阿哈湖DOM的A峰变化不大),但在pHi≤5时又增大,这种现象表明随着pH值降低,腐殖酸和湖泊DOM中有机大分子发生卷曲,但在pH≤5时由于羧基的质子化又以平面伸展构型出现在溶液中.     

Effects of water chemistry and concentrations of dissolved organic matter on its fluorescence characteristics and molecular conformation

Previous studies showed that water chemistry and concentrations of dissolved organic matter (DOM) could affect its molecular conformation and binding characteristics with hydrophobic organic contaminants (HOCs). However, the conformational change of DOM resultant from water chemistry and concentrations of DOM was not extensively investigated; therefore, the contradictory reports regarding the binding property with HOCs were available in literature. In this study, the effects of ionic strength, pH and DOM concentrations on the fluorescence properties of two humic acids (HA), namely Fluka HA and Amherst HA, were investigated by three-dimensional excitation-emission matrix fluorescence spectroscopy (3DEEM) and steady-state fluorescence polarization (FP) techniques. The results not only corroborated previous observations obtained by other investigators, but revealed some new information about the fluorescence properties and molecular conformation of the humic acids under different water chemistry and DOM concentration conditions, which could shed light on its binding mechanisms and binding properties with HOCs.     

Sedimentary humic acid and fulvic acid as fluorescent organic materials

Fluorescence and absorption spectra of sedimentary humic acid (HA) and fulvic acid (FA), with molecular weights ranging from < 10,000 to >300,000, were measured at 20°C and pH 8. The maximum excitation and emission wavelengths of HA were longer than those of FA, being independent of molecular weight. The excitation and emission maxima can be utilized to differentiate between sedimentary HA and FA. It is suggested that the fluorophors in HA are of a higher molecular weight aromatic groups than those in FA.Smaller molecules were found to have a greater fluorescence than larger ones for sedimentary humic substances and this phenomenon is similar to those obtained for humic substances of terrestrial origin. The absorption coefficient (1/g/cm) of HA decreased, while that of FA increased with the increase in molecular weight. It was shown that fluorescence intensity per weight concentration unit of HA increases and that of FA decreases with increasing absorption coefficient.     

Marine Dissolved Organic Phosphorus Composition: Insights from Samples Recovered Using Combined Electrodialysis/Reverse Osmosis

The dominant phosphorus compound classes were characterized in marine samples using a new, high recovery method for isolating and concentrating bulk dissolved organic matter (DOM) called combined electrodialysis + reverse osmosis (ED/RO). In contrast to earlier studies that use ultrafiltration (UF) to recover only the high molecular weight DOM, ED/RO is capable of isolating both low molecular weight (LMW) and high molecular weight (HMW) DOM. Samples were collected from a broad range of marine environments: along a transect incorporating coastal and offshore waters off the Southeastern United States, in Effingham Inlet, a Pacific fjord located on Vancouver Island, British Columbia and in the Amundsen Sea, Antarctica. Results from phosphorus nuclear magnetic resonance (³¹P NMR) analysis reveal a similar abundance of P compound classes among samples, phosphate esters (80–85%), phosphonates (5–10%) and polyphosphates (8–13%). These samples contain significantly higher proportions of polyphosphate P and P esters and lower proportions of phosphonates than measured in previous studies using the UF method. The much higher levels of polyphosphate detected in our samples suggests that polyphosphate is present mainly in the LMW dissolved matter fraction. Polyphosphates in dissolved matter may be present as (or derived from) dissolved nucleotides or organismal polyphosphate bodies, or both. Low molecular weight P esters are possibly composed of phosphoamino acids and small carbohydrates, like simple sugar phosphates and/or dissolved nucleotides. Phosphonates in DOM are more prevalent as HMW phosphonate compounds, which suggests that LMW phosphonates are more readily utilized in marine ecosystems. Overall, the investigation of DOM across a size spectrum that includes both the HMW and the LMW fractions reveals a new picture of phosphorus distribution, cycling and bioavailability.     

Interaction of Cr(III) with the humus acids of soil,water, and bottom sediments

The interaction of Cr(III) with humus acids [fulvic (FA) and humic (HA) acids] was studied in the systems Cr(III)-FA, Cr(III)-HA, and Cr(III)-FA-HA. Chromium(III) reacts with FA extracted from the headwaters of the Moscow River and from the Krapivenka River (a tributary of Lake Seliger) to form a highly soluble high-molecular-weight Cr(III)-hydroxofulvate complexes with \(\bar \beta _{11} \) = 1.93 × 10⁶ and 5.70 × 10⁶, respectively. Humic acids extracted from peat in the Tver area and the sapropel of Lake Seliger behave as complexing sorbents with conditional affinity constants logβ = 3.78 and 3.23 for Cr(III) sorption at HA sites in the peat and sapropel, respectively. In the three-component system Cr(III)-FA-HA, the Cr(III) distribution coefficient between solution and precipitate is controlled by the pH value and FA content in the solution and decreases by 1–1.5 orders of magnitude with increasing fulvic acid content.     

The lignin component of humic substances: Distribution among soil and sedimentary humic,fulvic, and base-insoluble fractions

Vanillyl, syringyl and cinnamyl phenols occur as CuO oxidation products of humic, fulvic and base-insoluble residual fractions from soils, peat and nearshore marine sediments. However, none of these lignin-derived phenols were released by CuO oxidation of deepsea sediment or its base-extractable organic fractions. Lignin analysis indicated that peat and coastal marine sediments contained significantly higher levels of recognizable vascular plant carbon (20–50%) than soils and offshore marine sediments (0–10%).Although accounting for less than 20% of the total sedimentary (bulk) lignin, lignin components of humic acid fractions compositionally and quantitatively resembled the corresponding bulk samples and baseinsoluble residues. Recognizable lignin, presumably present as intact phenylpropanoid units, accounted for up to 5% of the carbon in peat and coastal humic acids but less than 1% in soil humic acids. Fulvic acid fractions uniformly yielded less lignin-derived phenols in mixtures that were depleted in syringyl and cinnamyl phenols relative to the corresponding humic acid fractions.Within the vanillyl and syringyl families the relative distribution of acidic and aldehydic phenols is a sensitive measure of the degree of oxidative alteration of the lignin component The high acid/aldehyde ratios and the low phenol yields of soils and their humic fractions compared to peat and coastal sediments indicate extensive degradation of the lignin source material. Likewise, the progressively higher acid/aldehyde ratios and lower phenol yields along the sequence: plant tissues (plant debris)-humic acids-fulvic acids suggest that this pattern represents the diagenetic sequence for the aerobic degradation of lignin biopolymers.     

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.     

Early diagenesis of fatty acids and isoprenoid alcohols in estuarine and coastal sediments

Fatty acids and isoprenoid alcohols were analyzed in river, estuarine, and coastal sediment cores: (1) to investigate the distribution of these lipids among the unbound phase. those bound or closely associated with humic substances, and those bound or closely associated with the huminkerogen and clay mineral matrix. (2) to investigate the diagenetic changes of these lipids with depth in the sediments. and (3) to obtain information on the use of these compounds as organic tracers in marine sediments.Results confirm earlier observations that fatty acids are rapidly altered in marine sediments Both the total and the individual fatty acids decrease in concentration with depth in the sediments: unsaturated acids decrease faster than saturated acids and unbound acids decrease faster than bound acids Approximately 8–62% of the fatty acids were unbound. 2–22% were associated with humic substances. and 38–86% were associated with the residual organic-mineral matrix. Qualitative differences also exist between the fatty acids associated with the unbound, humic, and residual fractions. The ratio of trans/cis geometric isomers of the fatty acids generally increases downcore. with no rearrangement of the double bond positions within the molecules. Either the cis isomer is being preferentially degraded with depth in the sediments, or there is a low temperature, clay catalyzed conversion of the cis isomers to the trans isomers occurring down the cores.Phytol was the major alcohol present in the sediments and does not appear to be altered as rapidly as the fatty acids. Less than 10% of the total phytol (PHY) plus dihydrophytol (DHP) was present as DHP and no trend could be discerned between PHY and DHP with depth or with unbound, humic, and residual material in the cores. All of the isolated DHP appeared to be present as the RRR stereoisomer. Along with the absence of phytane in the cores, this observation suggests that the reduction of phytol to dihydrophytol is microbially mediated in the upper layer of the sediment.     

Arsenic distribution in the dissolved, colloidal and particulate size fraction of experimental solutions rich in dissolved organic matter and ferric iron

Due to the widespread contamination of groundwater resources with arsenic (As), controls on As mobility have to be identified. In this study we focused on the distribution of As in the dissolved, colloidal and particulate size fraction of experimental solutions rich in ferric iron, dissolved organic matter (DOM) and As(V). Size fractions between <5 kDa and >0.2 μm were separated by filtration and their elemental composition was analyzed. A steady-state particle size distribution with stable element concentration in the different size classes was attained within 24 h. The presence of DOM partly inhibited the formation of large Fe-(oxy)hydroxide aggregates, thus stabilized Fe in complexed and colloidal form, when initially adjusted molar Fe/C ratios in solution were <0.1. Dissolved As concentrations and the quantity of As bound to colloids (<0.2 μm) increased in the presence of DOM as well. At intermediate Fe/C ratios of 0.02-0.1, a strong correlation between As and Fe concentration occurred in all size fractions (R² = 0.989). At Fe/C ratios <0.02, As was mainly present in the dissolved size fraction. These observations indicate that As mobility increased in the presence of DOM due to (I) competition between As and organic molecules for sorption sites on Fe particles; and (II) due to a higher amount of As bound to more abundant Fe colloids or complexes <0.2 μm in size. The amount of As contained in the colloidal size fractions also depended strongly on the initial size of the humic substance, which was larger for purified humic acids than for natural river or soil porewater samples. Arsenic in the particle size fraction >0.2 μm additionally decreased in the order of pH 4 ? 6 > 8. The presence of DOM likely increases the mobility of As in iron rich waters undergoing oxidation, a finding that has to be considered in the investigation of organic-rich terrestrial and aquatic environments.     

Characteristics of normal fatty acids from sediments as a function of geologic-geochemical factors

Forty-nine samples from Mesozoic rocks of Northern Bulgaria and from recent marine muds of the Black Sea have been analyzed for fatty acids (FA), using extraction, treatment with ion exchange resin and gas chromatography. There is a higher concentration of normal (n) FA in the recent marine sediments, as well as in their bitumen extracts than in the rocks as a whole. There is twice as much n-FA in the rocks containing dispersed organic matter (DOM) formed mainly by benthonic organisms as compared to ancient sediments with planktonic DOM. The content of n-FA has decreased nine and five times, respectively in planktonic DOM in the sequence: limestones-marls-argillites and clayey siltstones, while the amount of organic carbon has risen four and two times. The n-FA are chiefly represented by C₁₆ and C₁₈ and in the recent sediments also by C₂₂ molecules. However when the level of maturity of DOM corresponds to the katagenetic degrees of MK₃ and MK₄, maximum is in n-FA with 19 and 20 carbon atoms. A gradual decrease in the amount of the n-FA with even-numbered carbon atoms was noted as maturity of the planktonic DOM increases from early diagenesis in recent marine sediments to the katagenetic degrees of MK₃ and MK₄ in ancient rocks. The ratios $\text{FA}\text{HC}$ and $\text{FA}\text{HC}\text{+ FA}$ have also decreased when the katagenetic maturity of DOM changes from PK₃ degree to MK₄ degree. These geochemical features may be used as an additional criterion in determining the principal phase of oil formation.     

Humic acids in brown coals from the southern Russian Far East: General characteristics and interactions with precious metals

Brown coals with high Au and PGE concentrations from six deposits in the southern Russian Far East were analyzed for elemental composition, acid-base properties, and the molecular-size distribution of humic acids (HA). The ash contents of the coals were determined to be negatively correlated with their Au concentrations, and the content of “organic Au” (which is chemically bound to humic substances, HS) reaches 95%. The most probable mode of Au occurrence in the brown coals is submicrometer-sized particles of elemental gold stabilized by HA. Quantum-mechanical calculations of interactions between Au(0) clusters with model HS fragments confirm that HS could be originally strongly chemically adsorbed on the surface of elemental gold particles. Different stability of colloids during centrifuging of alkali extracts of the gold-bearing brown coals was proved to be likely responsible for the selective separation of free HA and those bound with gold particles, and this can be used to develop a technology for gold recovery from coals without decomposing their organic matrix.     

[1H] and [13C]NMR studies on the importance of aromatic structures in fulvic and humic acids

To obtain information on the contribution of aromatic fragments to the chemical structure of humic substances, we carried out a study on the [¹H]NMR and [¹³C]NMR spectra of humic and fulvic acids and their oxidative degradation products extracted from an Andosol soil.[¹H]NMR spectra of all organic fractions present considerable adsorption between 7.4 and 8.8 ppm, due to the presence of aromatic protons.The percentages of aromatic protons in respect to the total amount of protons are as follows: FA 20%, HA 19%, degraded FA < 12%, degraded HA 14%. The values indicate that the contribution of aromatic structures to the humic substances is significant, also considering that they are highly substituted.The degraded fractions contain smaller amounts of aromatic protons, because degradation causes the opening of the aromatic rings. Thus results obtained from the degradation do not seem to be reliable for defining the importance of aromatic structures in humic substances.Also the [¹³C]NMR spectra show signals in the aromatic region which derive from unsubstituted carbon atoms, while signals originating from tertiary carbon atoms merge with the noise. We believe that, at present, [¹H]NMR spectroscopy is more suited for studying the role played by aromatic compounds in organic soil fractions.     

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.     

Organic matter-metal interactions in Recent sediments: the role of humic substances

Atomic emission spectrographic analysis of the trace inorganic constituents of marine humic substances gave the following range of concentrations: Si, 200 ppm to > 2%; Al, 400 ppm to ~ 1%; Fe, 600–3000 ppm; Ca, 600 ppm to > 2%; Mg, 20–6000 ppm; Na, 600 ppm to > 2%; Ag, < 6–600 ppm; B, < 60–1000 ppm; Cu, 600–4000 ppm; Mn, 8–100 ppm; Mo, <20–3000 ppm; Ni, 100–1000 ppm; Pb, < 40–600 ppm; Sn, 40–600 ppm; Ti, < 20–2500 ppm; V, 20–200 ppm; Zn, 350–4500 ppm; Zr, < 60–500 ppm.Humic substances contain a sizeable portion of the Cu, Mo and Zn found in sediments, but are less important for Ni, Co and Pb, and are insignificant for the Mn, V and Fe content. The metals are mostly introduced into the humates during their diagenetic formation in sediment by dissolution of metals from various mineralogical phases. A precursor of the sedimentary humates, the polymeric organic material dissolved in interstitial water, contains most of the Cu and Zn, about half of the Ni, Fe and Co, and very little of the Mn found in interstitial water. Comparison of the data on humates with that obtained by H₂O₂ treatment of sediments indicates that Cu, Zn and possibly most of the Mo are associated with organic matter, but that Ni and Co are associated with sulfides.     

桂林毛村岩溶区自然植被土壤团聚体中腐殖质组成初步研究

探索土壤有机碳物理保护与化学保护的关系,有助于揭示土壤固碳和培肥机理,明确不同粒级团聚体和不同腐殖物质组分对土壤固碳和肥力的贡献。本研究对岩溶区自然植被土壤团聚体中腐殖质含量进行了研究,结果表明:(1)灌丛和林地土壤团聚体中有机碳含量总体上均表现为随着土层深度的增加逐渐下降,而在不同土层深度随着团聚体粒径范围的变化则有机碳含量的变化规律则不同,无明显一致的规律;(2)两种土地利用方式各粒径团聚体中胡敏酸和富里酸均比全土小。这可能是由于在湿筛分离团聚体的过程中溶于水的那部分胡敏酸和富里酸成分被损失掉;(3)各腐殖质组分随着团聚体粒径范围的减小在两种自然植被上均无明显一致的规律,但胡敏酸和富里酸总量则基本表现为随着团聚体粒径范围的减小而逐渐升高,即在0.25mm和0.5~0.25mm粒径范围团聚体中最大;(4)两种自然植被土壤各土层中和各团聚体中胡敏酸/富里酸(HA/FA)基本上表现为小于1,这主要是因为研究区温度相对较高,湿度较大,植被覆盖度大,微生物降解作用强所致。     

Molecular formulae of marine and terrigenous dissolved organic matter detected by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

The chemical structure of refractory marine dissolved organic matter (DOM) is still largely unknown. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS) was used to resolve the complex mixtures of DOM and provide valuable information on elemental compositions on a molecular scale. We characterized and compared DOM from two sharply contrasting aquatic environments, algal-derived DOM from the Weddell Sea (Antarctica) and terrigenous DOM from pore water of a tropical mangrove area in northern Brazil. Several thousand molecular formulas in the mass range of 300-600 Da were identified and reproduced in element ratio plots. On the basis of molecular elemental composition and double-bond equivalents (DBE) we calculated an average composition for marine DOM. O/C ratios in the marine samples were lower (0.36 ± 0.01) than in the mangrove pore-water sample (0.42). A small proportion of chemical formulas with higher molecular mass in the marine samples were characterized by very low O/C and H/C ratios probably reflecting amphiphilic properties. The average number of unsaturations in the marine samples was surprisingly high (DBE = 9.9; mangrove pore water: DBE = 9.4) most likely due to a significant contribution of carbonyl carbon. There was no significant difference in elemental composition between surface and deep-water DOM in the Weddell Sea. Although there were some molecules with unique marine elemental composition, there was a conspicuous degree of similarity between the terrigenous and algal-derived end members. Approximately one third of the molecular formulas were present in all marine as well as in the mangrove samples. We infer that different forms of microbial degradation ultimately lead to similar structural features that are intrinsically refractory, independent of the source of the organic matter and the environmental conditions where degradation took place.