Optical characteristics and solar photodegradation of dissolved organic matter in Arkansas River, USA

Dissolved organic matter （DOM）, a mixture of numerous organic compounds of 30 to 300000 D, exists in all natural water resources including rivers, lakes and oceans, and plays a very important role in global carbon cycle and ecology. The DOM molecules absorb UV light strongly in short wavelengths and prevent microorganisms from being damaged by solar UV irradiation. Meanwhile, the large DOM molecules are then photodegraded into inorganic carbon and smaller organic molecules which are easier for bacterioplankton to digest. The Arkansas River is one of the largest rivers in the US, and a major input of organic materials to the Mississippi River and Gulf of Mexico. However, the photochemical properties of the DOM in the river water have not been investigated. To study this photodegradation process of the Arkansas River, water samples from the river were collected, filtered, sealed into quartz flasks, and exposed to sunlight for up to 15 hours. Some samples were retrieved from the flasks at certain time intervals. The intensity of the sunlight was measured during the exposure process at 30 min to 1 hr intervals. UV-vis absorption, fluorescence emission, 3D fluorescence spectra and DOM concentrations were determined for all retrieved samples. It was found that the total DOM concentration decreased while the dissolved inorganic carbon （DIC） concentration increased in the samples. UV absorption and fluorescence intensity of DOM decreased exponentially. The disappearance rate of UV absorption varied with wavelength. The loss of integral fluorescence was about 2.6 times that of the UV absorption at the excitation wavelength. In addition, the quantum yields also decreased, and the peak position of 3D fluorescence scan shifted to shorter wavelength.     

Determination of Hg and MeHg complexation with dissolved organic matter by fluorescence quenching titration

In natural waters inorganic mercury （Hg） and methylmercury （MeHg） are complexed with a variety of inorganic and organic ligands, such as OH^-, Cl^-, sulfide, thiols, and dissolved organic matter （DOM）. The bioavailability and toxicity of Hg and MeHg are related to their speciation, instead of their total concentrations. Among these species, Hg-DOM and MeHg-DOM complexes are the least known, due to the complexity and site-specificity of DOM in natural waters. Here we report the complexation between DOM and Hg or MeHg using fluorescence spectroscopy. The Suwannee River fulvic acid, peat humic acid, amino acid typotophan, and natural organic matter from the Suwannee River, Nordic River, and Delta Marsh were studied at their respective excitation/emission maxima,     

Mechanism of removing dissolved organic matter （DOM） by poly-silicic-ferric sulfate （PSF） coagulant

Chemical coagulation is very important in water treatment and was primarily designed for particle and turbidity removal. However, the concentration of dissolved organic matter （DOM） in drinking water and wastewater sources has increased greatly due to the development of industries and agricultures. Generally, the removal of DOM by conventional coagulation is not high, so enhanced coagulation has become a widely used method in developing or developed countries, in which a new type of efficient coagulant is developed as a cheap, practical and reasonable method. It has been widely recognized that the removal of DOM by iron-based coagulants is superior to that by aluminum salts. As a new type of inorganic polymer of iron-based salt, poly-silicic-ferric sulfate （PSF） has been studied since the late 20th century in Japan, but the mechanism of removing DOM still only concerns the essential recognition including adsorption/charge-neutralization, bridging, sweeping and so on. In this investigation, PSF was prepared by a particular co-polymerization method. The oxidization of PSF on humic acid （HA）, the hydrolysis law of PSF and the adsorption of HA on kaolin were studied. The characteristics [microstructure, size of species, Zeta potential and oxidation-reduction potential （ORP）] and coagulation performance of PSF were explored as compared to those of polyferric aluminum （PFA）. Mechanism of removing DOM （surrogated by humid acid （HA）） by PSF was analyzed primarily in terms of oxidization, hydrolysis species distribution, characteristics and coagulation behavior. The results showed that PSF is an oxidization coagulant and may change the molecular structure of HA, thus modifying the nature of HA surface and the nature of the interface between HA and water solution, and transforming the hydrophilic characteristics of HA into hydrophobic, thus improving the adsorption of HA. Different pH values give different influences on the complexation mode between HA oxidized by PSF, PSF and kaolin.     

Origin and three-dimensional fluorescence spectrum of the chromophoric dissolved organic matter in Yangtze estuary, East China

Dissolved organic matter （DOM） is an important chemical component in natural water. Chromophoric dissolved organic matter （CDOM）, a fraction of optical properties, plays art important role in the biogeochemical cycle of nutrients in aquatic environment. People realized that DOM cycle is crucial in the global carbon and nitrogen flux, and also is inherently related to nutrients and trace metal elements. Therefore, CDOM was concerned by scientists in global oceanography and limnology fields. Water samples were collected from three sections （North Channel, South Channel and Zhuyuan） of the Yangtze （Changjiang River） estuary in March 2006 Three-dimensional excitation emission matrix （3-DEEM） fluorescence spectra were analyzed for those filtrates through Whatman GF/F filters. Dissolved organic carbon （DOC） was also measured by TOC analyzer. The tidal variety was also taken into account. The 3-D EEM fluorescence scans suggested the fluorescence characteristics of humic acid （Ex=332-344 nm, Em=439-451 nm） and fulvic acid （Ex=250-254 nm, Em=472-478 nm） were obvious, and the fluorescence group of protein-like and tyrosine （Ex=230 nm, Em=283 nm） was also found. They are mainly composed of CDOM in the Yangtze estuary. Further data analysis, especially the fluorescence index （f 450/500）, showed that terrestrial signal was rather strong （1.41-1.65） in the surface water, however, some terrestrial CDOM signals of bottom water showed excursions （1.28-1.39）. On the other hand, anthropogenic sign was impressed in the waters of Zhuyuan, which is one of the main drain outlets of Shanghai Metropolis. DOC concentrations ranged from 2.2 mg/L to 3.4 mg/L in Zhuyuan and South Channel, and from 2.0 mg/L to 2.4 mg/L in North Channel. The tide effect played a role in the composition of the CDOM measured by 3-D fluorescence scan technology.     

Ultraviolet absorbance titration for the determination of conditional stability constants of Hg（Ⅱ） and dissolved organic matter

Strong interaction between natural dissolved organic matter （DOM） and Hg（Ⅱ） may influence the transport, conversion, toxicity and bio-validity of mercury in the environment. In this paper ultraviolet （UV） absorbance titration was employed for the first time for the determination of the conditional stability constants of Hg（Ⅱ） and （DOM）. With increasing Hg（Ⅱ） concentrations, the UV absorbance of fulvic acid, humic acid, and DOM in river increases progressively. By linear and non-linear model fitting, the conditional stability constants （lgK） of Hg（Ⅱ） and DOM were worked out to be 3.54-4.93 and 3.64-4.85, respectively. The results are consistent with those acquired by the typical fluorescence quenching titration method, with the maximum relative error of lgK being 2.6% and the average relative error being 0.2%. The UV absorbance titration method has the advantages of rapid determination, simple performance, and it will probably become a new approach to studying interactions between DOM and trace metallic ions.     

Profiling of dissolved organic compounds in the oil sands region using complimentary liquid–liquid extraction and ultrahigh resolution Fourier transform mass spectrometry

Understanding and characterizing organics in aquatic environments is a great challenge for environmental monitoring, especially for the oil sands industry due to the complexity and potential toxicity of dissolved organics in water. To date, significant efforts have been made in investigating the toxicity of naphthenic acids, although other compounds may also contribute to the toxicity of oil sands process-affected water (OSPW). Here, we present a case study showing a systematic approach for profiling the organic composition of OSPW and environmental water samples by concentrating and separating dissolved organics through complementary liquid–liquid extractions followed by positive- or negative-ion mode ultrahigh resolution mass detection. Our comparative investigation shows clear differences in the composition of dissolved organics (homologues particularly) not only between OSPW samples and environmental water samples, but also differences among oil sands operators. Sulfur-containing compounds (especially the SO _n classes) appear to have great potential to be used for evaluating the impact of OSPW, while our understanding of oxygen-only containing compounds should not be limited to O₂ (i.e., classic naphthenic acids), but rather can be broadened to include many other compound classes (for instance O _n , n = 1–9). Systematic profiling of water samples should be more widely implemented for monitoring the origin and transport of organics in aquatic ecosystems of the oil sands development region, northeastern Alberta, Canada.     

Emerging organic contamination in China

Persistent Organic Pollutants （POPs） have caused great public concern during the past decade. To address this global public concern, China joined international forces to sign a groundbreaking United Nations treaty in Stockholm, known as the Stockholm Convention. The Chinese Government agreed to reduce and eliminate the production, use or release of 12 key POPs. Because the convention specifies a scientific review process for all other compounds, the addition of other POPs of global concern to the list in the future is also possible. The most possible candidate compounds are some species used as polybrominated flame retardant and perfluronated compounds, called emerging chemicals. Most emerging chemicals are those with POP-like characteristics, they are persistent in the environment; travel over long distances via air and water; toxic and bioaccumulating in living things. Those chemicals pose an unacceptable threat to human health and the environment.     

Reconstruction of climatic change quantitatively with dissolved noble gases in groundwaters

One kind of climatic proxies only can describes the comparative change of temperature or rainfall, but dissolved noble gases in groundwater can be used to date groundwater, calculate temperature and rainfall, and this method can give the exact change value of three parameters in one time. Dissolved noble gases in groundwater has four sources, radioactivity-formed noble gases which are from radioactive decay of some radioactive elements in the aquifers, balance-dissolved noble gases from dissolved air in balance condition in the course of supplying, excess noble gases from excess air for groundwater-air mixing and water table changing during infiltrating, and outer-interfused noble gases from outer interfusing air in open conditions during runoff. Because the contents of radioagenic noble gases in groundwater are correlated to flowing time, such as He, the age of groundwater can be dated with 4He based on the solubility of He and the radioactive intensity of aquifers. The solubility of noble gases is the function of temperature. We can compare the contents of balance-dissolved noble gases in groundwater with the temperature-solubility experimental curves of noble gases, and calculate the forming temperature of groundwater. The contents of excess noble gases are related to the water column of infiltration which can reveal the volume of rainfall in a given period of time in general, and it may increase along with the pressure of aquifers when groundwater table rises greatly. So we can calculate the value of rainfall by comparing the contents of excess noble gases in groundwater samples with those in modem groundwater. Reconstruction of climatic change on a quantitative basis with the method of dissolved noble gases in Hebei plain （China） shows that the temperature changed from 3.8 to 19.7℃ in the past forty thousand years, it decreased to 3.8℃ in 16000 a B.P. but higher than 19.7℃ in 5060 a B.P. The rainfall was about 600mm during 40000 to 15000 a B.P., then decreased gradually to 410mm in 11000 a B.P., but subsequently increased to 950mm in 4400 a B.P. The change of noble gas temperature is consistent with 180 shift, and 6D varied with the change of other climatic proxy, such as rainfall.     

Oxidative dissolution of metacinnabar (β-HgS) by dissolved oxygen

The oxidative dissolution rate of metacinnabar by dissolved O₂ was measured at pH ∼5 in batch and column reactors. In the batch reactors, the dissolution rate varied from 3.15 (±0.40) to 5.87 (±0.39) × 10⁻² μmol/m²/day (I=0.01 M, 23°C) and increased with stirring speed, a characteristic normally associated with a transport-controlled reaction. However, theoretical calculations, a measured activation energy of 77 (±8) kJ/mol (I=0.01 M), and the mineral dissolution literature indicate reaction rates this slow are unlikely to be transport controlled. This phenomenon was attributed to the tendency of the hydrophobic source powder to aggregate and minimize the effective outer surface area. However, in a column experiment, the steady-state dissolution rate ranged from 1.34 (±0.11) to 2.27 (±0.11) x 10⁻² μmol/m²/day (I=0.01 M, 23°C) and was also influenced by flow rate, suggesting hydrodynamic conditions may influence weathering rates observed in the field. The rate of Hg release to solution, under a range of hydrogeochemical conditions that more closely approximated those in the subsurface, was 1 to 3 orders of magnitude lower than the dissolution rate due to the adsorption of released Hg(II) to the metacinnabar surface. The measured dissolution rates under all conditions were slow compared to the dissolution rates of minerals typically considered stable in the environment, and the adsorption of Hg(II) to the metacinnabar surface further lowered the Hg release rate.     

14C in bicarbonate and dissolved organics—a useful tracer?

The tunnel excavation at the Äspö Hard Rock Laboratory opened several fracture zones at various depths in the crystalline bedrock. One of these zones is the `Redox zone', a vertical fracture zone penetrated at 70 m depth. Except for the tunnel intersection, several boreholes were drilled to intersect the zone at various depths (ranging from 5 to 70 m) and distances from the tunnel. The response in groundwater chemistry to the opening of the zone has been monitored in these boreholes during 3 a, starting in 1991 and for the boreholes at 70 m depth the monitoring is still ongoing. The water chemistry during this monitoring can be largely explained by mixing between fresh water and native saline groundwater (4900 ppm Cl⁻). An increase in HCO⁻₃ was recorded, which was interpreted as due to anaerobic respiration. This was supported by ¹⁴C-contents in dissolved organic Carbon and HCO⁻₃, indicating that recent organic C is transported into the zone and oxidised to CO₂. This study exemplifies the use of ¹⁴C-analyses of HCO⁻₃ in order to trace different C sources contributing to the HCO⁻₃ in the groundwater. Three sources were identified: (1) dissolved CO₂, dominantly soil-CO₂ possibly with some contribution of atmospheric CO₂; (2) dissolution of calcite, with low ¹⁴C content, which dominantly occurs in the near-surface recharge area; and (3) oxidation of organic material through anaerobic respiration. Corrections for ¹⁴C and HCO⁻₃ in the native saline water made it possible to determine 2 different fresh water components corresponding to different flow paths. The C isotope data are in accordance with the results from the tracer test and the groundwater flow model, and support that the extensive build up of HCO₃⁻ does not mainly takes place locally within the zone but is transported into the zone by dominantly lateral flow. The results from the monitoring showed that new hydrochemical stability is established, which also comprises the interaction between the organic and inorganic C cycles.     

Punctual and continuous estimation of transit time from dissolved organic matter fluorescence properties in karst aquifers,application to groundwaters of ‘Fontaine de Vaucluse’ experimental basin (SE France)

For about 10 years, environmental tracing development using dissolved organic matter (DOM) has been the subject of several studies. Particularly, the use of characterization techniques, like fluorescence emission–excitation matrices has enabled the identification of DOM sources and monitoring them within mainland or marine hydrosystems. Moreover, hydrogeologists have shown the significance of total organic carbon content used as a fast seepage tracer in karstic aquifers. The aim of this study consists in using DOM fluorescence signals to develop a transit time semi-quantitative tracer in heterogeneous hydrosystems. The Low-Noise Underground Laboratory (Vaucluse, France) cuts the network of Fontaine de Vaucluse (FV) karstic vadose zone randomly, and offers a special access to different unstructured dripwaters, with different hydrodynamic behaviour, inside its galleries, i.e. not hierarchical as in natural caves. Previous long-term hydrodynamic and hydrochemical studies allowed the understanding of their hydrogeological behaviour and the estimation of mean transit times. That is why this site is adequate to develop new transit time tracers. After identification of the different DOM sources (i.e. lithic and rendzic leptosols), fluorescence intensities monitoring from soil leachates and dripwaters, for certain excitation–emission wavelength pairs, allowed the development of punctual transit time tracing, by spotting infiltration periods of fluorescent compounds, and monitoring their transfer within a hydrosystem. A fluorescence index (humification index) and the mean transit time of each gallery groundwater, stemmed from previous hydrodynamic and hydrochemical studies, allowed the calibration of a logarithmic relationship. This one allows the development of a continuous transit time tracing method that estimates transit times without long-term studies. It has been tested on two springs of FV catchment basin, providing transit time estimations for karstic hydrosystems that do not present a mixture between recent and pluriannual waters.     

Migration of nutrients dissolved by precipitation and their role in soil erosion

The aim of this research is to study the change of P and N contents of the surface runoff and subsurface flow caused by rainfall events, from the watershed till the stream. Samples were taken and analyzed from the surface runoff water after each rainfall …     

Trace metals in particulate and dissolved phases in Victoria Harbour, Hong Kong

Marine water samples, including both surface and bottom samples, were collected from the five sampling sites in Victoria Harbour during December 2004 and February 2005. The concentrations of trace metals （Cd, Co, Cr, Cu, Ni, Pb and Zn） in the suspended particulate matter （SPM） and dissolved phases as well as the Pb isotopic compositions of the suspended particulates were determined to assess the potential sources and transport pathways of metal contaminants in the harbour. The results showed that sewage discharges along the harbour dominated the SPM loadings in water, particularly in the dry season. The total concentrations of Co, Cr, Cu, Ni and Zn in water showed a close association with the SPM loadings, indicating that SPM was important in transporting these metals in the coastal environment. Dissolved phase was predominant for Cd in Victoria Harbour. The particulate phase was the major form of Pb in marine water.     

Matrix protected organic matter in a river dominated margin: A possible mechanism to sequester terrestrial organic matter?

The provenance of organic matter in surface sediments from the northern Gulf of Mexico was investigated by analyzing the compositions of lipid biomarkers (n-alkanes, fatty acids, sterols) liberated after a series of chemical treatments designed to remove different organo-mineral matrix associations (i.e. freely extractable, base-hydrolyzable, unhydrolyzable). Bulk analyses of the organic matter (carbon content, carbon:nitrogen ratios, stable and radiocarbon isotopic analyses) were also performed on the intact sediments and their non-hydrolyzable, demineralized residue. We found recognizable lipids from distinct sources, including terrestrial vascular plants, bacteria and marine algae and zooplankton, within each of the isolated fractions. Based on the lipid signatures and bulk compositions, the organic matter within the unhydrolyzable fractions appeared to be the most diagenetically altered, was the oldest in age, and had the highest abundance of terrigenous lipids. In contrast, the base-hydrolyzable fraction was the most diagentically unaltered, had the youngest ages and was most enriched in N and marine lipids. Our results indicate that fresh, autochthonous organic matter is the most important contributor to base-hydrolyzable lipids, whereas highly altered allochthonous sources appear to be predominant source of unhydrolyzable lipids in the surface sediments from the Atchafalaya River shelf. Overall, the lipid biomarker signatures of intact sediments were biased towards the autochthonous source because many of the organic compounds indicative of degraded, terrigenous sources were protected from extraction and saponification by organo-mineral matrices. It is only after these protective matrices were removed by treatment with HCl and HF that these compounds became evident.     

Do organic ligands affect calcite dissolution rates?

Steady state Iceland-spar calcite dissolution rates were measured at 25 °C in aqueous solutions containing 0.1 M NaCl and up to 0.05 M dissolved bicarbonate at pH from 7.9 to 9.1 in the presence of 13 distinct dissolved organic ligands in mixed-flow reactors. The organic ligands considered in this study include those most likely to be present in either (1) aquifers at the conditions pertinent to CO₂ sequestration or (2) soil/early diagenetic environments: acetate, phthalate, citrate, EDTA⁴⁻, succinate, d-glucosaminate, l-glutamate, d-gluconate, 2,4-dihydroxybenzoate, 3,4-dihydroxybenzoate, fumarate, malonate, and gallate. Results show that the presence of <0.05 mol/kg of these organic anions changes calcite dissolution rates by less than a factor of 2.5 with the exception of citrate and EDTA⁴⁻. The presence of 0.05 mol/kg citrate and EDTA⁴⁻ increases calcite dissolution rates by as much as a factor of 35 and 500, respectively, compared to rates in organic anion-free solutions. Further calcite dissolution experiments were performed in the presence of organic polymers similar to bacterial exudates, cell exopolysaccharides, and analogs of microbial cell envelopes: alginate, lichen extract, humic acid, pectin, and gum xanthan. In no case did the presence of <100 ppm of these organics change calcite dissolution rates by more than a factor of 2.5. Results obtained in this study suggest that the presence of aqueous organic anions negligibly affects calcite forward dissolution rates in most natural environments. Some effect on calcite reactivity may be observed, however, by the presence of organic anions if they change substantially the chemical affinity of the fluid with respect to calcite.     

Do organic ligands affect forsterite dissolution rates?

Far-from equilibrium, steady state forsterite dissolution rates were measured at pH ∼3 and 25 °C in aqueous solutions containing 0.1 m/kg NaCl and up to 0.1 mol/kg of 13 distinct dissolved organic ligands in mixed-flow reactors. The organic ligands considered in this study include those common in Earth surface environments and those considered as potential catalysts for use in CO₂ sequestration efforts: acetate, oxalate, citrate, EDTA⁴⁻, glutamate, gluconate, malonate, aspartate, tartrate, malate, alginate, salycilate and humate. The presence of up to 0.1 mol/kg of each organic ligand altered forsterite dissolution rates less than 0.2 log units, which is the estimated uncertainty of the measured rates. Results obtained in this study, therefore, suggest that the presence of aqueous organic anions negligibly affects forsterite far-from equilibrium dissolution rates in most natural environments, and indicate that forsterite carbonation may not be appreciably accelerated by organic ligand catalysis.     

Phosphorus features in FT-IR spectra of natural organic matter

Fourier-Transform Infrared （FT-IR） spectroscopy has been used extensively to characterize natural organic matter （NOM）. Absorption bands at 1100-1000 cm^-1 in the FT-IR spectra of NOM have been frequently assigned to alcoholic and polysaccharide C-O stretching or to vibrations of SiO2-related impurities. However, these interpretations do not consider that a strong band associated with P-O bonds of phosphate also appears in the same region. We evaluated the correlation between absorbance in this region and P content of 19 NOM samples from terrestrial, aquatic and plant shoot sources. In the spectra of 10 humic and fulvic acid samples, shoulder to minor bands appeared around 1050 cm^-1. Absorbance intensity at 1050 cm^-1 （Y） was linearly related to P content （X） by the following： Y=4.38X＋0.3 l, with R2=0.90. We did not observe such a close correlation between absorbance and P content in two aquatic NOM samples. Apparently, this is because the aquatic NOM samples were concentrated by reverse osmosis, which would have concentrated not only humic and fulvic acids but also other soluble organic solutes present in natural waters. In the FT-IR spectra of seven dissolved organic matter （DOM） samples obtained from dried plant shoots, broad and/or multiple bands around 1075 cm^-1 were observed with a shoulder at 977 cm^-1. These characteristics were more like those of organic phosphate compounds （such as inositol hexaphosphate）. However, solution 31P nuclear magnetic resonance spectroscopic analysis showed no significant amount of organic phosphate present in these samples.     

Characterization of combined organic–inorganic acid-pretreated cassava stem

A number of previous studies established that the autoclave-mediated pretreatment enabled the efficient way of producing fermentable sugars from lignocellulosic residues. Hence, our emphasis was on studying the surface morphology of cassava stem to reveal its complex internal structure. In this study, combined organic (oxalic)–inorganic (sulfuric) acid was utilized for the pretreatment of cassava stem at 121 °C and 1 bar of pressure for 15 min. For the pretreatment, mixture containing 10 mL of 1% (w/v) of oxalic acid and 1% (w/v) sulfuric acid (5 mL each) was added to 1 g cassava stem and autoclaved. Pretreated samples were characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD) and ultraviolet spectroscopy (UVS). FTIR spectral studies confirmed the removal of hemicellulose and lignin from the pretreated cassava stem (PCS) when compared with untreated cassava stem. SEM micrographs revealed the decimation in the surface of cassava stem after pretreatment. XRD motifs shown that crystallinity index of PCS decreased from 63 to 52%. Thus, this study established the structural modifications to unlock its valuable components for further applications.     

Studying of quality parameters and organic contaminants in honey samples

Honey is valuable food for mankind since the ancient times. It was the only sweetener till the start of the industrial sugar mass production. As honey plays an important role in our nutrition and its positive effects on health is well known, it is very important to study the nutritional properties and the origin of different honey samples. The usually determined quality parameters of honey： pH values, water content, sugar content, acidity, HMF content, enzyme activity, pollen content, amino acid content, ash content, etc. It is also important to know the content of the organic contaminants in honey. A short time ago there were some quality problems with Hungarian and Greek honey in the European Union. A toxic material （para-dichlorobensene） was found in honey originated from Greece. The amount was higher than the allowable limit in the EU. Therefore, it is necessary to build up a good and applicable traceability system for honey. During the past few years the traceability concept has become increasingly familiar in many sectors of the food industry. Traceability is an essential tool for ensuring both production and product quality. The opportunity to connect traceability with the whole documentation and control system represents an effective means for boosting the consumer＇s perception of a food＇s safety and quality. In our work we have done, which quality parameters can be used for a good identification system.     

Forms and bioavailability of phosphorus associated with natural organic matter

Natural organic matter （NOM） is an important ingredient in soil which can improve physical, chemical, and biological properties of soils and nutrient supplies. In this study, we investigated the spectral features and potential availability of phosphorus （P） in the IHSS Elliott Soil humic acid standard （EHa）, Elliott soil fulvic acid standard Ⅱ （EFa）, Waskish peat humic acid reference （WHa）, and Waskish peat fulvic acid reference （WFa） by fluorescence spectroscopy, FT-IR, solution 31P NMR, 3-phytase incubation and UV irradiation. We observed more similar spectral features between EHa and EFa as well as between WHa and WFa than between the two humic acids or two fulvic acids themselves. Phosphorus in WHa and WFa was mainly present in the orthophosphate form. However, only about 5% was water soluble. After treatment by both UV irradiation and enzymatic hydrolysis, soluble orthophosphate increased to 17% of WHa P, and 10%o of WFa P. Thus, it appears that a large portion of P in Waskish peat humic substances was not labile for plant uptake. On the other hand, both orthophosphate and organic phosphate were present in EHa and EFa. Treatment by both UV irradiation and enzymatic hydrolysis increased soluble orthophosphate to 67% of EHa P and 52% of EFa P, indicating that more P in Elliott soil humic substances was potentially bioavailable. Our results demonstrated that source （soil vs. peat） was a more important factor than organic matter fraction （humic acid vs. fulvic acid） with respect to the forms and lability of P in these humic substances.