Huminstoffe in Sedimentporenwässern ausgewählter Bundeswasserstraßen

Humic substances are an important component of organic carbon in natural waters. Their character and properties are determined by the sources and the processes of their origin. Humic substances are not exclusively refractory compounds, but they are involved in several transformation processes in the water. It is not possible to directly analyze humic substances, therefore several methods were applied for their characterization. The presented LC-OCD-technique is a size-exclusion-chromatography with online UV- and carbon detection. Carbon fractions, e.?g. humic substances were differentiated by their molecular size. The portion of humic substances in sediment porewaters of the rivers Elbe, Rhine, Danube, Oder, Müritz-Elde-Waterway was determined. With only a few exceptions it ranges from 50 to 67?% of the dissolved organic carbon. The high molecular weight fraction accounts for 10 to 34?%, and the fraction of the low molecular weight substances was from 7 to 37?%. The ratio between the spectral absorption coefficient (254?nm) and the organic carbon is called SUVA (L/mg × m) and is an inidicator of the proportion of unsaturated bonds in the humic substances. Both high molecular herbal components (e.?g. cellulose, lignin) and biological degradiation products (e.?g. amino acids, sugar) are involved in sediment porewater transformation and degradiation processes. This demonstrates the distribution of the dissolved organic carbon between the fractions.     

Effect of iron addition on the performance of anoxic-oxic membrane process and biological phosphorus removal北大核心CSCD

In order to solve the problem of poor treatment of phosphorus in membrane bioreactor (MBR) with long sludge retention time (SRT), a ferric salt was added to enhance phosphorus removal; FeCl36H2O (Fe/P = 2.0) was added to the reactor. The removal efficiency of nitrogen, organic matters, and phosphorus in the MBR was investigated systematically. Moreover, this study focused on the membrane performance, the change of active sludge flora, and the effect of adding a ferric salt on membrane fouling before and after the addition. It was seen that adding the ferric salt could not affect the removal of COD and NH4 +-N and the removal rate of COD and NH4 +-N reached over 90%. However, the average removal rate of phosphorus was 52%, while the removal rate increased by nearly 40% after adding the ferric salt. The effects of adding ferric salts on the dominant bacteria and biological phosphorus removal of activated sludge were further studied. The results showed that the addition of ferric salt (Fe/P = 2.0) decreased the diversity of active sludge flora and relative abundance of some phosphorusaccumulating organisms and had a negative effect on biological phosphorus removal. The analysis of transmembrane pressure difference (TMP) recording revealed that the concentration of iron salts did not exacerbate membrane fouling. The results showed that the concentration of iron salts entering the membrane bioreactor would reduce the relative abundance and phosphorus removal efficiency of the activated sludge in the system to a certain extent, but it had no obvious effect on membrane fouling. It allowed the effluent to attain acceptable standards, especially with respect to phosphorus removal efficiency. © 2018 Science Press. All rights reserved.     

气浮中试工艺中若干运行参数

为找出气浮(DAF)工艺的最佳运行工艺参数,对影响气浮工艺出水效果较大的预处理条件、混凝剂投量、水力负荷、水力条件、回流比、刮渣周期等运行参数做了大量的中试试验研究,发现适当的预臭氧处理可以提高UV254的去除,预加氯可以提高对浊度和藻类的去除,预加高锰酸盐可以提高对浊度、藻类、嗅味和UV254等的去除,预加粉末活性炭可以提高对有机物、色度、嗅味的去除,混凝剂投量从10 mg/L增加到50 mg/L,气浮工艺对有机物的去除率提高了30%~40%,水力负荷越高气浮出水浊度越高,回流比越大气浮出水浊度越低,气浮池过长的刮渣周期也会降低出水水质。总之,合理调整气浮池的工艺参数,可以提高气浮出水水质,降低运行成本。     

Variation in humic and fulvic acids during thermal sludge treatment assessed by size fractionation,elementary analysis,and spectroscopic methods

Thermal pretreatment can be applied to sludge anaerobic digestion or dewatering. To analyze the variation in humic substances during thermal sludge treatment, sludge humic and fulvic acids were extracted before and after 30-min thermal treatment at 180℃, and then their contents, molecular weight distributions, elementary compositions, and spectral characteristics were compared. The results showed that the total contents of humic and fulvic acids in the sludge almost remained constant during thermal treatment, but 35% ofhumic and fulvic acids were dissolved from the sludge solids. Moreover, both humic and fulvic acids were partly decomposed and 32% of humic acids were converted to fulvic acids. The median value of the molecular weights of humic acids decreased from 81 to 41 kDa and that of fulvic acids decreased from 15 to 2 kDa. Besides the reduction in molecular size, the chemical structures of humic and fulvic acids also exhibited a slight change, i.e. some oxygen functional groups disappeared and aromatic structures increased after thermal sludge treatment.     

Application of ultra-sonication,acid precipitation and membrane filtration for co-recovery of protein and humic acid from sewage sludge

A novel method was applied to co-recover proteins and humic acid from the dewatered sewage sludge for liquid fertilizer and animal feed. The proteins in sewage sludge were first extracted using the processes of ultra-sonication and acid precipitation, and then the humic acid was recovered via membrane filtration. The extraction efficiency was 125.9 mg humic acid?g⁻¹VSS volatile suspended solids (VSS) and 123.9 mg proteins?g⁻¹ VSS at the optimal ultrasonic density of 1.5 W?mL⁻¹. FT-IR spectrum results indicated that the recovered proteins and humic acid showed similar chemical characteristic to the natural proteins and humic acid. The acidic solution (pH 2) could be recycled and used more than 10 times during the co-recovery processes. In addition, the dewatered sludge could be easily biodegraded when the humic acid and proteins are extracted, which was essential for further utilization. These findings are of great significance for recovering valuable nutrient from sewage sludge.     

Unwanted metals and hydrophobic contaminants in bioreactor effluents are associated with the presence of humic substances

Biological treatment of landfill leachate is challenging due to the presence of complex compounds. Here, we treated an old landfill leachate using a membrane bioreactor under the following conditions: 24 h for hydraulic retention, 65 days of sludge retention and an average organic load rate of 1.71 ± 0.16 g/L/day. We observed a high removal of ammonia, phosphorous and some metals. However, removal of organic carbon was incomplete. Despite a major removal of suspended solids, hydrophobic and volatile hydrophilic compounds, high concentration of fulvic acid and hydrophilic contaminants was found in the effluent. Overally, we demonstrate that the presence of humic substances in the effluent is associated with the detection of arsenic, copper and chromium and di(2-ethylhexyl) phthalate.     

沙土不同有机组分对磷的解吸特征影响

采用平衡解吸法研究了沙土不同有机组分对磷的解吸附特征影响。结果表明,通过过氧化氢去除有机质后的沙土使磷的解吸比例（Dr=0.94）大幅度增加,解吸迟滞性指数（TⅡ=0.05）显著降低;有机质是影响磷在沙土上解吸特征的重要因素;磷在橡胶态胶体（轻组有机组分）上的表面分配作用吸附是导致解吸比例（Dr=0.81）增大,解吸迟滞性指数（TⅡ=0.05）减小的原因;稳结态腐殖质中的胡敏酸在对磷的吸着和滞留过程中发挥重要作用,HⅡ＋HⅢ组（Dr=0.57、TⅡ=0.30）;磷在紧结态腐殖质所形成的团聚体结构中引起的团聚体结构不可逆形变是导致磷的解吸比例（HⅢ组Dr=0.24）降低,解吸迟滞性指数（HⅢ组TⅡ=0.49）增大的根本原因,考查土壤磷的解吸特征不但要考虑有机质的含量,更要考虑有机质的存在形态,它也是影响土壤磷解吸特征的重要因素,轻组有机组分、重组有机组分、以及重组有机组分中的稳结态腐殖质、紧结态腐殖质所携载的吸附态磷进入水体后对上覆水体的释放通量可分别按其饱和吸附量的81%、66%、57%和24%进行估算。     

First determination of Cu adsorption on soil humin

Humic substances are heterogeneous mixtures of organic compounds occurring in huge amounts mainly in waters, soils, sediments and organic wastes. They are formed during the decay of living organisms. They play a very important role in many environmental processes including carbon sequestration, water cleaning and retention, soil erosion, fertility and pollutant retention. However, due to their complex nature, humic substances are still poorly characterized and much less known than living matter. Humin is the most insoluble and, in turn, the least understood fraction of humic substances. To our knowledge, no information is currently available on the adsorption and desorption behaviors of metal ions on soil humin. Here, we report the adsorption and desorption properties of Cu(II) on humin and humic acids isolated from a forest soil in northeast China using the batch equilibration method. Solid-state ¹³C cross-polarization magic angle spinning nuclear magnetic resonance (¹³C CPMAS NMR) spectroscopy was used to characterize and compare the chemical structures of humin and humic acid. The batch experiments’ results show that humin has a lower adsorption capacity and higher adsorption reversibility for Cu(II) than humic acid. The adsorption isotherms well fitted both the Langmuir and Freundlich equations. Humin, therefore, plays an important role in controlling the fate, transport and bioavailability of Cu(II) in the environment. The ¹³C CPMAS NMR spectra showed that compared with humic acid, humin was higher in alkyl C, carbohydrate C and phenolic C and was lower in methoxyl C, aryl C and carbonyl C. These findings mean that humin was less alkylated, more aliphatic and more hydrophobic.     

Effect of long-term application of corn stalks and inorganic fertilizers on fluorescence characteristics of water extractable organic matter in a meadow black soil of northeast China

ABSTRACT

Returning crop residues into fields, either alone or in combination with inorganic fertilizer, is considered as a practical way to enhance soil fertility. However, information concerning the effects of crop residues and inorganic fertilizer application on water extractable organic matter (WEOM) in soil is scarce. The aim of this study was to examine the 10-year effect of corn residue (CR) return with or without the application of nitrogen, phosphorus, and potassium (NPK) fertilizer on the quantity and quality of WEOM in a black soil of northeast China by means of ultraviolet absorbance, fluorescence excitation--emission matrix, and derived spectroscopic indices. The application of NPK fertilizers and CR, alone or together, increased the content of total soil organic carbon (SOC), water extractable organic carbon (WEOC), and ratio of WEOC/SOC, with the sequence being NPK + CR > CR > NPK > CK. Compared with control treatment, the individual application of NPK fertilizer decreased the aromaticity of WEOM. In contrast, elevated proportion of tryptophan-like fluorophore and microbially derived fulvic acid-like components with low molecular weight was detected in the WEOM. The amendment with CR alone resulted in increase in aromaticity of WEOM and proportion of plant-derived humic acid-like component with large molecular weight, accompanied by reduced proportion of tyrosine-like compounds. For the soil with CR restoration, the application of NPK fertilizer increased aromaticity of WEOM, and large molecular weight fulvic acid-like and humic acid-like compounds were found. However, the proportions of tyrosine-like and tryptophan-like compounds were diminished. The quantitative and qualitative analysis of WEOM using fluorescence spectroscopy describes responses to be observed in long-term different fertilization strategies.     

UV light induces Ag nanoparticle formation: roles of natural organic matter,iron, and oxygen

Nanoparticles occurring in the environment originate either from engineered, synthetically produced nanoparticles, or from naturally produced nanoparticles. The latter can be formed in natural media by light-induced reduction of metal ions in presence of natural organic matter, such as humic substances occurring widely in waters, soils and sediments. There is actually few knowledge on the effect of sunlight and of the nature of organic matter on nanoparticle formation. Therefore, we studied here the photoreduction of silver(I) ion to silver nanoparticles with and without ferrous ion under oxic and anoxic conditions, using humic and fulvic acids as proxies of natural organic matter. UV light-induced formation of silver nanoparticles was monitored up to 60 min by measuring surface plasmon resonance in air-saturated mixture and nitrogen-saturated mixture of silver(I) ion–organic matter. Results show that the surface plasmon resonance intensity was about 2.5 times higher in the nitrogen-purged solution mixture than the air-saturated solution. This finding suggests the oxygen-containing species had no major role in forming silver nanoparticles. Therefore, photo-driven formation of silver nanoparticles most likely involved photoactivation of silver(I) ion and natural organic matter complexes. We observed also that both iron(II) and iron(III) ions highly modified the surface plasmon resonance spectra of the particles with broader features. Results also reveal that in the presence of humic acid, the intensity of the surface plasmon resonance peak decreased by at least 50 %, while almost no change in the intensity was seen when fulvic acid was used. Overall, our findings demonstrate that the ligand–metal charge transfer process, affected by the nature of organic matter, i.e., humic acid versus fulvic acid, was influenced by redox iron species.     

Humic substances as surfactants

Humic substances from soils and sediments can be defined as surface active substances based on the surface tension measurements. Although there are several micellar structural models of humic substances currently available, few studies evaluating humic substances as surfactants have been conducted to date. Therefore, we evaluated the ability of humic substances and their derivatives to influence surface tension. We found that the ability of a humic substance to influence the surface tension of a solution depends on its origin. Many industrially produced humic materials exerted little or no impact on surface tension, whereas humic substances isolated from natural environments (water, soil, peat, sediments, sludge from wastewater treatment facilities) exerted a large impact on surface tension. These findings indicate that the modification of humic substances can enable their use as surfactants. In addition, these findings indicate that solutions of humic substances and their derivatives can be used to increase the solubility of organic compounds.     

Arsenic in drinking water and mortality in the Southern Great Plain,Hungary

Arsenic distribution has been found in drinking waters. A connection between arsenic and other constituents of water was determined. Close positive correlation was found between arsenic and humic substances over most of the study area. In two smaller areas, there was no correlation between arsenic and humic substances. In these waters, the arsenic distribution is not controlled by organic matter, but by other factors which need further investigations.Examination of mortality in the populations consuming water containing levels of arsenic above and below that permitted did not show any significant differences in standardised mortality ratio (SMR) from all causes of death for both male and female. The SMR from the main causes of death — diseases of the circulatory system and neoplasms — shows controversial results for males and females.     

不同农业施肥制度对红壤稻田土壤磷肥力的影响

采用田间定位试验研究了几种不同农业施肥制度对红壤稻田土壤磷肥力的影响．结果表明：（1）在移耕农业、施化学N肥和NK胆施肥制下，农田系统磷素亏缺量大，7年间达140mg/hm2以上，土壤有效磷降低；（2）有机农业和施化学P肥施肥制可促进农田系统磷素平衡，改善土壤供磷状况，提高稻株含磷量和磷累积量；（3）在有权无机结合施肥制下，农田系统土壤磷素盈余量大，7年间共达200mg／hm2以上，并可改善土壤磷组分，增加土壤有效磷含量，促进水稻对磷的吸收．     

Photoreactivity of humic substances: relationship between fluorescence and singlet oxygen production

Humic substances are natural compounds abundantly present in the environment. They play a significant role in the natural attenuation of pollution in surface water due to their capacity to generate reactive species upon solar light excitation. Finding physico chemical parameters related to this property would be of a great help in the prediction studies of the organic pollutants fate. In this work, we investigated relationships between the ability of the humic substances to produce singlet oxygen and their fluorescence properties. For this, a series of sixteen humic acids, fulvic acids, and water-extractable organic matter from soils were studied. The steady-state singlet oxygen concentrations in the irradiated humic substances solutions were measured by monitoring the loss of furfuryl alcohol added as a singlet oxygen scavenger. The emission spectra of the sixteen samples were also recorded. Values of the steady-state singlet oxygen concentrations and the emission intensities showed significant variations among the humic samples and a parallel increase. Thus, here we demonstrate that the rate of singlet oxygen production and the emission intensity of the humic samples are correlated, the best correlation being obtained for emission wavelengths between 500 and 580 nm. This correlation which was never reported until now can be used to estimate the singlet oxygen-production capacity of the humic substances based on their fluorescent properties.     

聚合氯化铝/壳聚糖复合絮凝剂在活性污泥中的调理作用

考察了聚合氯化铝、壳聚糖以及复合絮凝剂对活性污泥的调理作用,结果表明,它们都有助于改善活性污泥的脱水,通过比较污泥比阻的变化,观察试验中的矾花生成现象,表明聚合氯化铝/壳聚糖复合絮凝剂在污泥调理中不仅效果明显,污泥比阻最先达到低点3×1012m·kg-1,滤速较快,而且有助于减少金属污泥的生成,是较佳的调理剂.     

垃圾渗滤液中有机物分子量的分布及在MBR系统中的变化

利用凝胶层析方法分析了垃圾渗滤液中有机物分子量的分布情况,并考察了利用膜生物反应器(MBR)处理垃圾渗滤液系统中有机污染物分子量的分布以及水溶性腐殖质(AHS)含量的变化．研究发现,垃圾渗滤液中的有机物主要由两部分组成,即分子量大于6000的大分子物质和分子量小于1500的小分子物质．大分子物质主要是水溶性腐殖质,而小分子物质主要由挥发性有机酸及水溶性腐殖质组成．大分子的AHS难以被微生物降解,但能被微滤膜截留．大部分小分子的AHS既难以被微生物降解,又不能被膜截留,是构成MBR处理出水COD的主要成分．     

交替冻融对东北典型土壤腐殖质的影响

以受季节性冻融过程影响显著的东北地区的黑土、暗棕壤和水稻土为例,采用实验室模拟的方法,研究交替冻融循环过程（分别在-20℃和20℃下处理）对土壤腐殖质的影响。研究表明：交替冻融后,黑土和暗棕壤松结态腐殖质质量分数分别增加了39%和28%,HA/FA分别上升了45%和35%;水稻土松结态腐殖质质量分数和HA/FA分别下降了18%和31%。三维荧光结果进一步验证,黑土、暗棕壤在交替冻融中土壤芳香化程度增高,HA/FA上升,而水稻土则相反。黑土和暗棕壤松结态腐殖质和HA/FA升高,主要是微生物分解作用和土壤大团聚体破坏等原因造成,水稻土松结态腐殖质和HA/FA降低,主要是水稻土的缺氧环境造成。     

有机肥施用对珠三角菜地土壤磷污染风险的初步研究

通过田间小区试验研究有机肥施用量对菜心产量、土壤磷形态的影响,分析土壤磷形态之间的相关性,评估菜地红壤磷污染风险。结果表明,有机肥施用并未提高菜心的产量和生物量,而超过一定使用量之后,反而降低菜心产量和生物量;土壤无机磷形态以Fe-P和Al-P为主,占土壤无机磷质量分数的90%以上。有机肥施用提高土壤各形态无机磷的质量分数,且有机肥用量越高,土壤Fe-P、Al-P、Ca-P和O-P质量分数越高。有机肥过量施用显著提高土壤速效磷和水溶性磷质量分数;分别对Olsen-P和CaCl2-P与各形态磷进行逐步回归分析,只有Olsen-P和CaCl2-P与Ca-P具有线性关系（p〈0.05）,方程为Y1=36.95＋0.622 1X,Y2=-0.102 5＋0.048 6X。表明施用有机肥下,Ca-P是菜地土壤有效磷的最直接来源,可以作为红壤磷污染风险评价指标。     

Diazinon leaching through a sandy soil amended with different humic materials

The water leaching of diazinon (O,O‐diethyl‐O‐2‐isopropyl‐6‐methylpyrirnidin‐4‐yl phosphoroth‐ioate) through soil columns, was studied after column amendments with two well characterized humic acids (HA), in both liquid and solid state, and with the original raw organic materials, an oxidized coal and a leonardite, from which the HA were extracted. The percolation curves and the pesticide distribution over the soil columns showed that the addition of the raw organic materials and the solid HAs reduced significantly the mobility of the pesticide along the soil column. The oxidized coal was more effective than the leonardite original material; the different origin of the two carbon‐rich materials had an influence on the diazinon movement along the soil columns and such difference was enhanced with increasing addition rates. Moreover, incubation at field capacity for two months of the soil columns treated with raw oxidized coal and leonardite, largely enhanced the described effects on pesticide behaviour. A complete adsorption of diazinon on columns and a practical absence of leaching was observed when the HA from both materials were added in dissolved form. These results were explained with the swelling of the humic micelles in water and the enhanced availability of inner hydrophobic surfaces for the strong adsorption of diazinon. The water diffusion into the solid humic materials after two months incubation, also explains their high pesticide retention capacity. This work indicates the usefulness of either solid o dissolved humic substances, with the proper hydrophobic character, in preventing the vertical leaching of non‐polar organic pesticides in soils.     

延边地区水稻稳产高产施肥体系的探讨

采用二次饱和D-最优设计,建立了有机肥、氮肥、磷肥和钾肥配合施用对水稻产量影响的数学模型.研究表明有机肥施用量的过多或过少均使水稻产量下降,化肥的施用也有相似的影响;有机肥与氮肥、磷肥、钾肥只有施用量在适宜的范围内,交互作用较大,产量最高.提出了延边地区水稻获得稳产、高产的施肥体系.