Soil organic matter chemistry. Part 1. Characterization of several humic preparations by proton and carbon‐13 nuclear magnetic resonance spectroscopy

Both laboratory and commercial preparations of humic substances (HSs) such as fulvic acids and humic acids along with HC1‐HF preparation of Manitoba peat soil organic matter were characterized using Fourier Transformation (FT) proton (¹H) and carbon‐13 (¹³C) nuclear magnetic resonance (NMR) spectroscopy. All the samples were dissolved in a solution of 0.4 N NaOD in D₂O. In the case of ‘H‐NMR spectroscopy, all the investigated humic samples displayed resonance absorption peaks in the region of 1–4 ppm indicating the likely presence of aliphatic protons in the preparations. However, with the exception of one fulvic acid preparation (extracted from Manitoba Carrol clay‐loam soil with 0.5 N NaOH), ¹H‐NMR spectra of all other samples provided evidence for strong aromatic character. The aliphatic and aromatic characteristics of such samples of HSs were further confirmed with the aid of ¹³C‐NMR spectra.     

镉对北京城郊土壤潜在硝化速率的影响

采集北京城郊5个区县的3种土壤褐土、潮土和山地棕壤,通过急性毒性实验,研究了外源添加镉(Cd)对土壤潜在硝化速率(PNR)的影响。结果表明,5个采样点土壤的PNR分别随土壤中总Cd和有效态Cd含量呈先增后减的趋势。所有处理土壤的有效态Cd含量与PNR的相关关系(R2=0.42,p0.001)优于土壤总Cd含量与PNR的相关关系(R2=0.27,p=0.001)。在土壤总Cd含量和PNR的逐步回归分析中,引入土壤有机质和阳离子交换量(CEC)2个变量可提高其相关性。基于土壤总Cd的EC50(PNR降低至对照50%时的土壤Cd浓度)和有效态Cd的EC50的最大值与最小值之间分别相差2.3倍和3.3倍,而EC10(PNR降低至对照10%的土壤Cd浓度)的最大值与最小值之间分别相差8.5倍和10.8倍。基于总Cd的EC50最低值出现在CEC最小的丰台土壤,而最高值出现在有机质含量最多的灵山土壤,但这2个EC50值未达到显著性差异,表明5个采样点的土壤有机质和CEC虽然在一定程度上影响Cd对PNR的毒性,但不足以引起EC50的显著变化。     

雄烯二酮在我国典型土壤中的吸附特性

采用批吸附室内模拟实验研究了雄烯二酮在我国红壤、潮土、黑土3种典型土壤中的吸附特征,以及牛粪溶解态有机质(DOM)对土壤吸附雄烯二酮的影响。结果表明,雄烯二酮在土壤中吸附动力学符合Elovch方程(R20.89),热力学特征可通过Freundlich等温吸附方程(R20.83)描述,土壤对雄烯二酮的吸附呈非线性吸附特征,其中潮土吸附等温线的非线性最强(n=0.37);吸附系数K f介于6.0~20.2,并与有机质含量呈显著正相关(p0.05)。雄烯二酮浓度较低时,共存牛粪DOM抑制其在土壤表面的吸附作用。研究认为,有机质是土壤吸附雄烯二酮的主要组分,共存牛粪DOM可促进雄烯二酮向地表水和地下水的迁移。     

Modeling the carbon dynamics of the La Grande hydroelectric complex in northern Quebec

A mechanistic semi-empirical carbon cycle model of the La Grande reservoir complex in northern Quebec, Canada was conceived in order to investigate the climate impact of such a large alteration of the continental water cycle. The model includes inputs from the drainage basin, organic matter release from flooded soils, CO₂ emissions across the water-atmosphere interface and sedimentation. Most input data stems from previous research by our group on those ecosystems. The model includes the seven reservoirs of the La Grande complex and was run for periods of 50 and 100 years. Terrigeneous dissolved, particulate and suspended soil carbon fluxes and concentrations were computed. Over 100 years, 31.3 × 10¹² g C are released from flooded soils, equivalent to 28-29% of inputs from the drainage basin. 40-74% of dissolved organic carbon is mineralized. CO₂ fluxes over 100 years are 50.5-79.8 × 10¹² g C, 46.4-67.9 × 10¹² g C more than in the absence of reservoirs. The increase in mineralization of organic matter and in CO₂ emissions is a result of the increase in cumulated water residence time due to the creation of the reservoirs. Changes in other carbon sinks and sources likely offset a part of this additional carbon flux to the atmosphere. In the first years following flooding of the reservoir, organic carbon release from flooded soils exceeds CO₂ emissions, implying the downstream export of large quantities of eroded soil organic carbon. After this initial period, CO₂ emissions are fuelled by organic carbon originating from the drainage basin.     

中国南方稻田土壤汞含量及潜在危害评价

选择我国南方水稻主产区安徽、浙江、湖南、湖北以及广西5个省,采集213个稻田土壤样品,探究我国南方稻田土壤中汞的空间分布特征与土壤理化参数(如p H值和有机质)的相关关系及汞富集的潜在危害。结果表明:不同省份的稻田土壤汞含量存在显著的差异(P0.05,n=213),含量范围是0.029~0.326 mg·kg~(-1)(干重),平均值为(0.094±0.036)mg·kg~(-1),与农用地土壤环境质量标准0.30 mg·kg~(-1)(GB15618—1995)相比,除湖北省以外均有轻度汞污染。Pearson相关性分析表明,稻田土壤中的汞含量与有机质含量呈显著正相关关系(P0.01,r=0.445),说明适度偏高的有机质有利于土壤汞的富集。不同省份稻田土壤潜在危害等级除浙江省外均在轻微到中等的范围内,浙江省的为强等级。     

Response of roselle (Hibiscus sabdariffa) to heavy metals contamination in soils with different organic fertilisations

The response of green roselle (Hibiscus sabdariffa) to Cu/Pb contamination and manure application in soil was investigated using pot experiments. Subsamples of a mineral soil were treated with increasing doses (0–500 mg kg^?1) of Cu/Pb only and/or amended (at 10% w/w) with poultry or swine manure. Roselle plants were grown, monitored for changes in growth rate and post-harvest aboveground dry biomass and tissue Cu/Pb concentrations were determined. The plants were typically greenish with linear growth profiles at all metal doses, indicating some level of tolerance. Dry biomass yields decreased as metal dose increased. Poultry manure enhanced roselle biomass yields better than swine manure. Tissue Cu/Pb concentrations increased linearly as metal doses increased in unamended soils; whereas nonlinear responses were observed in manure-amended soils. Soil-to-plant transfer factors, T _f (%) indicated that Cu (13≤T _f (% )≤60) was more phytoavailable to roselle than Pb (11≤T _f (% )≤20). Tissue metal concentrations were modelled from soil pH, organic matter, plant available and pseudototal metal; but the models appeared more reliable with plant available metal as a covariate than with pseudototal metal content. These observations may become useful whenever phytoextraction is the remedial option for soils moderately contaminated by toxic metals.     

Influences of Suspended Particles on the Runoff of Pesticides from an Agricultural Field at Askim, SE-Norway

Field and laboratory experiments were conducted to study the loss of particles from agricultural fields, and the role of suspended particles in carrying pesticides in surface runoff and drainage water. Propiconazole, a widely used fungicide was applied to experimental fields located at Askim, SE-Norway. Samples from surface runoff and drainage water were collected and analyzed for sediment mass, pesticides, particulate and dissolved organic carbon through a whole year. The surface soil and the runoff material were characterized by its particle size distribution, organic carbon content in size fractions and its ability to bind propiconazole. The results show that (1) particle runoff mostly occurred during the rainfall event shortly after harrowing in autumn. The highest particle concentration observed in the surface runoff water was 4600 mg l^–1, and in the drainage water 1130 mg l^–1; (2) the erosion of surface soil is size selective. The runoff sediment contained finer particle/aggregates rich in organic matter compared to its original surface soil; (3) the distribution coefficient (K _d) of propiconazole was significantly higher in the runoff sediment than in the parent soil. According to our calculation, particle-bound propiconazole can represent up to 23% of the total amount of propiconazole in a water sample with a sediment concentration of 7600 mg l^–1, which will significantly influence the transport behavior of the pesticide.     

Influence of human-induced disturbance on benthic microbial metabolism in the Pichavaram mangroves,Vellar–Coleroon estuarine complex,India

Large areas of mangroves in India are heavily disturbed by cattle grazing, hypersalinity, and other human-induced impacts. In two disturbed Avicennia marina forests and two undisturbed A. marina and Rhizophora apiculata forests in the Pichavaram mangroves of the Vellar–Coleroon estuarine complex, southeast India, we measured the rates and pathways of microbial decomposition of soil organic matter to determine if human impact is altering biogeochemical activity within these stands. Rates of total carbon oxidation (T_COX) were higher in the undisturbed A. marina forest (mean 199 mol C m^–2 year^–1) than in the two impacted stands (43 and 79 mol C m^–2 year^–1); rates of total carbon oxidation in the R. apiculata forest averaged 75 mol C m^–2 year^–1. Sulphate reduction (range 21–319 mmol S m^–2 day^–1) was the major decomposition pathway (65–85% of T_COX), except at the most disturbed forest (30% of T_COX). Rates of sulphate reduction at all sites peaked in sub-surface soils to a depth of about 1 m, leading to little carbon burial (3–5% of total C input). There was some evidence of measurable iron and manganese reduction in association with tree roots. Rates of microbial activity were rapid in comparison with rates measured in other mangrove soils, reflecting high rates of phytoplankton production and organic matter retention in this lagoon. Human-induced disturbance creates a sharp zonation of dry, hypersaline soil overlying less saline, wetter soil, suppressing surface microbial and root growth. We conclude that this vertical alteration of soil characteristics and biogeochemistry shifts the cycling of nutrients between trees and microbes to a disequilibrium state, partly explaining why mangroves are stunted in these declining forests.Communicated by G. F. Humphrey, Sydney     

Origin and Distribution of Suspended Organic Matter As Inferred From Carbon Isotope Composition in A Mediterranean Semi-Enclosed Marine System

Abstract

The origin and distribution of suspended organic matter, the trophic features and the stable carbon isotopic composition of particulate organic carbon (POC) were studied monthly in a Western Mediterranean semi-enclosed basin. Sampling stations were selected as a function of wind-exposure and the degree of vegetation cover and then compared with an adjacent unvegetated site. the predominant vegetation was seagrass (Posidonia oceanica and Cymodocea nodosa) and Caulerpa prolifera. Water samples were analyzed for total suspended matter (inorganic and organic fractions), photosynthetic pigments (chlorophyll-a and phaeopigments), dissolved organic carbon, particulate organic carbon and their isotopic composition. Temperature and salinity were also measured at the same sampling sites within range of Mediterranean limits. the suspended organic matter concentration was 1.77 ± 1.55 mg l^?1; the chlorophyll-a concentration was low (0.35 ± 0.24 μg l^?1); the disolved organic carbon concentration was 2,140 ± 2,010 μg l^?1; the particulate organic carbon concentration was 212 ± 106 μg l^?1 and the isotopic composition was 18.77 ± 2.51%_°. There were significant temporal differences except for phaeopigments, POC and its POC isotopic composition, and there were no spatial differences other than for δ¹³C. This picture highlighted a general seasonal trend and trophical features similar to adjacent sea.

Spatial differences in δ¹³C showed that the source of suspended organic matter was different between stations as that between sources and wind-hydrodynamic constraints. In     

Arachis hypogaea derived activated carbon steered remediation of Benzimidazole based fungicide adsorbed soils

Sorption characteristics of the Benzimidazole fungicide Carbendazim were assessed in seven different soils using batch equilibrium method and analysed by UV-Vis spectrophotometer. The values of adsorption co-efficient K_d ranged from 14.3 to 39.8?µg/mL depending upon unique physiochemical properties of soils. Negative values for Gibbs free energy (ΔG) proposed an exothermic and low interaction between Carbendazim and soil samples leading to physiosorption. Statistical analysis showed a negative correlation of soil pH and K_d (R²= ?0.80) and a positive correlation with organic matter (R^2?=?0.77). Activated carbon prepared from Arachis hypogaea (peanut shells) by acid activation for Carbendazim removal from soils was characterised by FTIR spectrometry, indicating the change in functional groups. The highest percentage removal observed was 70% in 5?ppm initial Carbendazim concentration while 65% in 7.5?ppm concentration. This method can be implied in agricultural soils as an efficient and cheap technique for removing the hazardous pesticides from the environment.     

Decomposition of silicate minerals by Bacillus mucilaginosus in liquid culture

The extraction of K⁺ and SiO₂ from silicate minerals by Bacillus mucilaginosus in liquid culture was studied in incubation experiments. B. mucilaginosus was found to dissolve soil minerals and mica and simultaneously release K⁺ and SiO₂ from the crystal lattices. In contrast, the bacterium did not dissolve feldspar. B. mucilaginosus also produced organic acids and polysaccharides during growth. The polysaccharides strongly adsorbed the organic acids and attached to the surface of the mineral, resulting in an area of high concentration of organic acids near the mineral. The polysaccharides also adsorbed SiO₂ and this affected the equilibrium between the mineral and fluid phases and led to the reaction toward SiO₂ and K⁺ solubilization. These two processes led to the decomposition of silicate minerals by the bacterium.     

Bioavailability of hydrophobic organic contaminants and quality of organic carbon

U.S. laws require that contaminant bioaccumulation potential be evaluated before dredged material can be recycled. Simple fugacity models, e.g. organic contaminant aqueous partition coefficient (K _oc)-derived theoretical bioaccumulation potential, are commonly used to estimate the partitioning of hydrophobic organic contaminants between sediment organic matter and organism lipid. K _oc-derived models, with or without the addition of a soot carbon term, did not accurately or consistently predict total polycyclic aromatic hydrocarbons (PAHs) and polychlorobiphenyls partitioning of eight sediments from ongoing dredging operations onto C₁₈-coated filter paper. These models also failed to predict the partitioning of individual PAHs from these eight sediments. These data underscore the trade-offs between the ease of using simple models and the uncertainty of predicted partitioning values.     

Variations between rice cultivars in root secretion of organic acids and the relationship with plant cadmium uptake

To attempt to understand certain mechanisms causing the variations between rice cultivars with regard to Cd uptake and accumulation, pot soil experiments were conducted with two rice cultivars at different levels of Cd, i.e., 0 (the control), 10, 50 mg Cd kg⁻¹ soil. The two rice cultivars differ significantly with regard to Cd uptake and accumulation. Root secretions of low-molecular-weight organic acids (LMWOA) for each treatment were measured with ion chromatography. The results showed that LMWOA concentrations in the soil planted with Shan you 63 (a high soil Cd accumulator) were all higher than those in the soil planted with Wu yun jing 7 (low soil Cd accumulator) at different soil Cd levels, although the magnitudes of the differences varied for individual LMWOA and depend on soil Cd concentrations. For all six LMWOA, there were significant differences at P < 0.05 or < 0.01 levels for soils treated with 10 and 50 mg kg⁻¹ Cd. The magnitude of the differences was greater under soil Cd treatments, especially at relatively low levels (for example, 10 mg Cd kg⁻¹ soil), than in the control. Acetic acid and formic acid constituted more than 96% of the total concentration of the six LMWOA, while citric acid constituted only about 0.1%. The rice cultivar with higher concentrations of LMWOA in soil accumulated more Cd in the plants. The results indicate that LMWOA secretion by rice root, especially in Cd-contaminated soils, is likely to be one of the mechanisms determining the plant Cd uptake properties of rice cultivars.     

Identification of Anthropogenic Organic Contamination Associated with the Sediments of a Hypereutropic Tropical Lake, Venezuela

The concentrations of organic carbon (Corg), inorganic carbon (Cinorg), organic nitrogen (Norg) and total aromatic (Arom_T) were determined in 25 samples of bottom sediments from the Lake Valencia, Venezuela, as a contribution to the knowledge about pollution by organic compounds in tropical lakes. Results demonstrate that the Corg and Norg concentrations do not show the pollution indexes by themselves. This is a consequence of the masking effect of naturally derived organic matter from the decay of algae and organisms in the water column and terrestrial plants, which are transported to the lake. Nevertheless, the Arom_T concentrations and the normalised Arom_T (normalized to organic carbon) make it possible to detect organic matter of anthropogenic origin, in the Arom_T levels are about nine times higher than those natural. The variation in the band intensity of the IRFT spectra for some functional groups present in the saturate and aromatic hydrocarbon fractions gives an indication of anthropogenic contribution for some zones of the lake. With the ¹H NMR spectra it was not possible to differentiate a natural source from an anthropogenic one in the lake. Naturally occurring organic compounds (eicosane, pentacosane, and hexacosane) were detected with GC technique in the saturated hydrocarbon fraction. The presence of an unresolved complex mixture (UCM) in the GC chromatograms indicates pollution by branched and cyclic hydrocarbons. These compounds are probably produced by the incomplete combustion of oil products. Potentially toxic organic compounds such as anthracene, phenanthrene and chrysene were found in the aromatic hydrocarbon fraction, which despite presenting low concentrations (ppb order) accumulate in the lake sediments along with the natural source organic matter. The main access paths of organic pollutants to the lake are the rivers which cross the two urban and industrial areas (Maracay and Valencia cities). The mixture of polluted sediments with bottom natural sediments and the autochthonous contribution of organic matter mitigate the pollution levels progressively towards the center of the lake.     

Effects of mussel (Perna canaliculus) biodeposit decomposition on benthic respiration and nutrient fluxes

Suspension-feeding bivalves increase the quantity and quality of sedimenting organic matter through the production of faeces and pseudofaeces that are remineralised in coastal sediments and thus increase sediment oxygen demand and nutrient regeneration. Bivalves are intensively cultivated worldwide; however, no bivalve biodeposit decay rates are available to parameterise models describing the environmental effects of bivalve culture. We examined sediment biogeochemical changes as bivalve biodeposits age by incubating coastal sediments to which we added fresh mussel (Perna canaliculus) biodeposits and measured O₂ and nutrient fluxes as well as sediment characteristics over an 11-day period. Biodeposits elevated organic matter, chlorophyll a, phaeophytin a, organic carbon and nitrogen concentrations in the surface sediments. Sediment oxygen consumption (SOC) increased significantly (P=0.016) by ∼1.5 times to 1,010 μmol m⁻² h⁻¹ immediately after biodeposit addition and remained elevated compared to control cores without additions for the incubation period. This increase is in the range of observed in situ oxygen demand enhancements under mussel farms. To calculate a decay rate for biodeposits in sediments we fitted a first-order G model to the observed increase in SOC. The significant model fit (P=0.001, r ²=0.72) generated a decay rate of 0.16 day⁻¹ (P=0.033, SE=0.05) that corresponds to a half-life time of 4.3 day. This decay rate is 1–2 orders of magnitude higher than published decay rates of coastal sediments without organic enrichment but similar to rates of decaying zooplankton faecal pellets. NH₄⁺ release increased rapidly on the day of biodeposit addition (P=0.013) and reached a maximum of 144 μmol m⁻² h⁻¹ after 5 days which was 3.6 times higher compared to control cores. During this period NH₄⁺ release was significantly (P<0.001 to P=0.043) higher in the cores with biodeposit additions than in control cores.     

Feeding biology of the brackish-water oncholaimid nematode Adoncholaimus thalassophygas

The brackish-water inhabiting nematode Adoncholaimus thalassophygas (De Man, 1876) may be classified as an omnivore and predator according to the gut contents of the adults. A series of ¹⁴C experiments was conducted to investigate the feeding potential of labelled microorganisms and dissolved ¹⁴C glucose. The observed consistent failure to incorporate ¹⁴C from labelled microorganisms, and its consistent success with dissolved ¹⁴C glucose suggests that dissolved organic matter may be more important than microorganisms as a food source for his nematode. This corresponds also with direct observations of living worms which showed very little uptake of particulate food other than that originating from predation. Defecation and mean gulping rates were low and, therefore, ¹⁴C glucose uptake from solution can hardly be explained by the assumption that large amounts of water are swallowed and passing through the gut. By means of mucus secretion, A. thalassophygas forms compact agglutinations of detrital sediment which are sites of enhanced microbial activity. We suggest that hatched juveniles feed primarily on dissolved organic matter released by the intensive microbial activity within this habitat. Adults retain the ability to utilize dissolved organic matter, and supplement their diet by scavenging on carcasses and occasional predation. Thus, the biology of oncholaimid nematodes may be characterized by an intimate linkage to microbial metabolism, although they do not appear to feed directly upon microorganisms.     

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.     

Heavy metals in soils and crops in Southeast Asia

In a reconnaissance soil geochemical and plant survey undertaken to study the heavy metal uptake by major food crops in Malaysia, 241 soils were analysed for cation exchange capacity (CEC), organic carbon (C), pH, electrical conductivity (EC) and available phosphorus (P) using appropriate procedures. These soils were also analysed for arsenic (As), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), mercury (Hg), nickel (Ni), lead (Pb) and zinc (Zn) using aqua regia digestion, together with 180 plant samples using nitric acid digestion. Regression analysis between the edible plant part and aqua regia soluble soil As, Cd, Cr, Cu, Hg, Ni, Pb and Zn concentrations sampled throughout Peninsular Malaysia, indicated a positive relationship for Pb in all the plants sampled in the survey (R ² = 0.195, p < 0.001), for Ni in corn (R ² = 0.649, p < 0.005), for Cu in chilli (R ² = 0.344, p < 0.010) and for Zn in chilli (R ² = 0.501, p < 0.001). Principal component analysis of the soil data suggested that concentrations of Co, Ni, Pb and Zn were strongly correlated with concentrations of Al and Fe, which is suggestive of evidence of background variations due to changes in soil mineralogy. Thus the evidence for widespread contamination of soils by these elements through agricultural activities is not strong. Chromium was correlated with soil pH and EC, Na, S, and Ca while Hg was not correlated with any of these components, suggesting diffuse pollution by aerial deposition. However As, Cd, Cu were strongly associated with organic matter and available and aqua regia soluble soil P, which we attribute to inputs in agricultural fertilisers and soil organic amendments (e.g. manures, composts).     

几类有机污染物的微塑料/水分配系数的线性溶解能关系模型

水体中的微塑料会吸附其中的有机污染物,影响有机污染物和微塑料的环境归趋和生态毒性。研究微塑料对有机污染物的吸附行为,对于评价有机污染物和微塑料的环境赋存、迁移及生物有效性有重要意义。污染物在微塑料与水之间的平衡分配系数(Kd),是表征微塑料对有机污染物吸附能力的重要参数。实验方法难以逐个测定众多有机污染物的Kd值,有必要发展其预测模型。本研究搜集了有机污染物的线性溶解能关系(LSER)参数及Kd值,构建了可预测有机污染物在聚丙烯微塑料与海水、聚乙烯微塑料与海水、聚乙烯微塑料与淡水之间Kd值的LSER模型。模型具有良好的拟合优度(R2adj介于0.794~0.903)、稳健性(Q2LOO和Q2BOOT分别介于0.763~0.863和0.720~0.804)和预测能力(R2ext和Q2ext分别介于0.886~0.971和0.825~0.954),能够用于预测多氯联苯、多环芳烃、六氯环已烷和氯苯类有机污染物的Kd值。