Tracking natural organic matter (NOM) in a drinking water treatment plant using fluorescence excitation-emission matrices and PARAFAC

Natural organic matter (NOM) in water samples from a drinking water treatment train was characterized using fluorescence excitation emission matrices (F-EEMs) and parallel factor analysis (PARAFAC). A seven component PARAFAC model was developed and validated using 147 F-EEMs of water samples from two full-scale water treatment plants. It was found that the fluorescent components have spectral features similar to those previously extracted from F-EEMs of dissolved organic matter (DOM) from diverse aquatic environments. Five of these components are humic-like with a terrestrial, anthropogenic or marine origin, while two are protein-like with fluorescence spectra similar to those of tryptophan-like and tyrosine-like fluorophores. A correlation analysis was carried out for samples of one treatment plant between the maximum fluorescence intensities (F_max) of the seven PARAFAC components and NOM fractions (humics, building blocks, neutrals, biopolymers and low molecular weight acids) of the same sample obtained using liquid chromatography with organic carbon detection (LC-OCD). There were significant correlations (p < 0.01) between sample DOC concentration, UVA₂₅₄, and F_max for the seven PARAFAC components and DOC concentrations of the LC-OCD fractions. Three of the humic-like components showed slightly better predictions of DOC and humic fraction concentrations than UVA_254. Tryptophan-like and tyrosine-like components correlated positively with the biopolymer fraction. These results demonstrate that fluorescent components extracted from F-EEMs using PARAFAC could be related to previously defined NOM fractions and that they could provide an alternative tool for evaluating the removal of NOM fractions of interest during water treatment.     

Understanding soluble microbial products (SMP) as a component of effluent organic matter (EfOM)

Formation of soluble microbial products (SMP) during biological degradation of organic compounds in a sequencing batch reactor (SBR) was investigated using high performance liquid chromatography--size exclusion chromatography (HPSEC) as well as other organic matter characterization tools. Results showed that carbon compounds in a glucose feed solution were totally transformed to other organic products classified biomass-associated products (BAP). The SMP-BAP contained in the SBR effluent consisted mainly of high-molecular weight (MW) fractions of organic matter, possibly originating from cell lysis. These compounds exhibited a low specific ultraviolet absorbance (SUVA) and a hydrophilic character. In addition, the characteristics of bulk effluent organic matters (EfOM) samples from wastewater treatment facilities were studied. It was observed that EfOM consisted of humic-like and hydrophobic (HPO) compounds, derived from the corresponding drinking water source, in addition to SMP-BAP. A superimposition of SEC chromatograms of the SMP-BAP and humic-like compounds represented a fingerprint of EfOM.     

Characterisation and removal of recalcitrants in reverse osmosis concentrates from water reclamation plants

Water reclamation plants frequently utilise reverse osmosis (RO), generating a concentrated reject stream as a by-product. The concentrate stream contains salts, and dissolved organic compounds, which are recalcitrant to biological treatment, and may have an environmental impact due to colour and embedded nitrogen. In this study, we characterise organic compounds in RO concentrates (ROC) and treated ROC (by coagulation, adsorption, and advanced oxidation) from two full-scale plants, assessing the diversity and treatability of colour and organic compounds containing nitrogen. One of the plants was from a coastal catchment, while the other was inland. Stirred cell membrane fractionation was applied to fractionate the treated ROC, and untreated ROC along with chemical analysis (DOC, DON, COD), colour, and fluorescence excitation-emission matrix (EEM) scans to characterise changes within each fraction. In both streams, the largest fraction contained <1 kDa molecules which were small humic substances, fulvic acids and soluble microbial products (SMPs), as indicated by EEM. Under optimal treatment conditions, alum preferentially removed >10 kDa molecules, with 17-34% of organic compounds as COD. Iron coagulation affected a wider size range, with better removal of organics (41-49% as COD) at the same molar dosage. As with iron, adsorption reduced organics of a broader size range, including organic nitrogen (26-47%). Advanced oxidation (UV/H₂O₂) was superior for complete decolourisation and provided superior organics removal (50-55% as COD).     

Long-term formation of microbial products in a sequencing batch reactor

Activated sludge in a sequencing batch reactor (SBR) is subjected to alternating feast-and-famine conditions, which may result in the enhanced production of microbial products: extracellular polymeric substances (EPS), soluble microbial products (SMP), and internal storage products (X_STO). In this work, the long-term formation of these three microbial products by activated sludge in an SBR is investigated using an expanded unified model with a parallel experimental study. We also use the model to compare the impacts in an SBR to those in a continuous-flow activated sludge system. The model captures all experimental trends for all components with solids retention time (SRT) for global steady state and within a cycle. At an SRT of 20 days, the active microorganisms constitute about 28% of the mixed liquor volatile suspended solids (MLVSS); the remaining biomass is comprised of residual inert biomass (X_I) of 40%, EPS of 31%, and X_STO of ∼1%. The active biomass becomes a smaller fraction with the increasing SRT, while the inert biomass becomes increasingly dominant. For soluble components, effluent chemical oxygen demand (COD) is dominated by SMP, which varies to some degree in a cycle, peaking as external substrate becomes depleted. Within the SBR cycle, external substrate (S) declines strongly in the first part of the cycle, and SMP shows a small peak at the time of S depletion. X_STO is the only biomass component that varies significantly during the cycle. It peaks at the time that the input substrate (S) is depleted. Simulation for a continuous-flow activated sludge system and comparison with an SBR reveals that the constant “famine” conditions of the continuous system lead to lower EPS and X_STO, but higher MLVSS and X_I.     

Similarities in effluent organic matter characteristics from Connecticut wastewater treatment plants

Effluent organic matter (EfOM) from five Connecticut (USA) municipal wastewater treatment plants was isolated with DAX8 (hydrophobic fraction) and XAD4 (transphilic fraction) resins. Isolate recoveries ranged from 18 to 42% of the total organic carbon for DAX8 resin and from 6 to 12% for XAD4 resin. Isolated EfOM was characterized by traditional organic geochemistry techniques. Weight-averaged molecular weights of extracted EfOM by size exclusion chromatography were 450-670 Da with higher weights observed for the hydrophobic fractions than the transphilic fractions. Fluorescence characterization showed both humic- and fulvic-like fluorescence, as well as tryptophan- and tyrosine-like fluorescence, the latter not commonly observed for terrestrial organic matter. Fluorescence indices were between 1.5 and 1.9 with lower values observed for hydrophobic EfOM fractions than for transphilic fractions. Specific ultraviolet absorbance was measured between 0.8 and 3.0 L mg⁻¹ m⁻¹ with higher values for the hydrophobic EfOM fractions. Together these results indicated that isolated EfOM is similar in characteristics to microbially derived organic matter from natural aquatic systems. Little variation in EfOM characteristics was observed between the five wastewater treatment plants, suggesting that the characteristics of EfOM are similar, regardless of treatment plant design.     

Effective removal of effluent organic matter (EfOM) from bio-treated coking wastewater by a recyclable aminated hyper-cross-linked polymer

Effluent organic matter (EfOM) is a complex matrix of organic substance mainly from bio-treated sewage effluent and is considered as the main constraint to further advanced treatment. Here a recyclable aminated hyper-cross-linked polymeric adsorbent (NDA-802) featured with aminated functional groups, large specific surface area, and sufficient micropore region was synthesized for effective removal of EfOM from the bio-treated coking wastewater (BTCW), and its removal characteristics was investigated. It was found that hydrophobic fraction was the main constituent (64.8% of DOC) in EfOM of BTCW, and the hydrophobic-neutral fraction had the highest SUVA level (7.06 L mg^?1 m^?1), which were significantly different from that in the domestic wastewater. Column adsorption experiments showed that NDA-802 exhibited much higher removal efficiency of EfOM than other polymeric adsorbents D-301, XAD-4, and XAD-7, and the efficiency could be readily sustained according to continuous 28-cycle batch adsorption–regeneration experiments. Moreover, dissolved organic matter (DOM) fractionation and excitation-emission matrix (EEM) fluorescence spectroscopy study indicated that NDA-802 showed attractive adsorption preference as well as high removal efficiency of hydrophobic and aromatic compounds. Possibly ascribed to the presence of functional aminated groups, relatively large specific surface area and micropore region of the unique polymer, NDA-802 possesses high and sustained efficiency for the removal of EfOM, and provides a potential alternative for the advanced treatment.     

Identifying the sources and fate of anthropogenically impacted dissolved organic matter (DOM) in urbanized rivers

Anthropogenic activities have dramatically changed the loads and compositions of dissolved organic matter (DOM) in urbanized streams. In this study, the spatial and temporal variations of DOM in the anthropogenically impacted Zhujiang River were investigated by analyzing the water samples in an upstream, urbanized area and downstream of the rivers on different days of one year. The results indicated that the levels of dissolved organic carbon (DOC) and total phosphorus (TP) were unaffected by seasonal changes, but the specific UV₂₅₄ absorbance (SUVA) values and the total nitrogen (TN) content were greater in the winter than those in the summer. Parallel factor (PARAFAC) analysis of the excitation emission matrices (EEM) revealed the presence of three anthropogenically derived components [tryptophan-like (C1) and tyrosine-like proteins (C3) and anthropogenic humic substances (C5)] in the urbanized rivers, and they had greater seasonal and spatial variability than the terrestrial and microbial humic substances (C2 and C4). Cluster analysis revealed that treated wastewater was an important source of DOM in the urbanized streams. Photodegradation experiments indicated that the DOM in the populous area of the rivers had greater photodegradation potentials than that in the downstream region or in the natural waters. Interestingly, that the anthropogenic humic substances (C5) were considerably more photoreactive than the other four PARAFAC components, which exhibited a decrease of 80% after exposure to sunlight for 0.5 d. This study suggests that the treated wastewater could be an important input to the DOM in the urbanized rivers and the naturally occurring photodegradation could help in eliminating the anthropogenic DOM during their transport.     

Filter pore size selection for characterizing dissolved organic carbon and trihalomethane precursors from soils

Filters with a pore size of 0.45 microm have been arbitrarily used for isolating dissolved organic carbon (DOC) in natural waters. This operationally defined DOC fraction often contains heterogeneous organic carbon compounds that may lead to inconsistent results when evaluating trihalomethane formation potential (THMFP). A finer pore size filter provides more homogeneous DOC properties and enables a better characterization of organic matter. In this study, we examined the effects of filter pore size (1.2, 0.45, 0.1 and 0.025 microm) on characterizing total organic carbon, ultra-violet absorbance at 254 nm (UV(254)) and THMFP of water extracts from a mineral and organic soil in the Sacramento-San Joaquin Delta, California. Results showed that the majority of water extractable organic carbon (WEOC) from these soils was smaller than 0.025 microm, 85% and 57% in organic and mineral soils, respectively. A high proportion of colloidal organic carbon (COC) in mineral soil extracts caused water turbidity and resulted in an abnormally high UV(254) in 1.2 and 0.45 microm filtrates. The reactivity of organic carbon fractions in forming THM was similar for the two soils, except that COC from the mineral soil was about half that of others. To obtain a more homogeneous solution for characterizing THM precursors, we recommend a 0.1 microm or smaller pore-size filter, especially for samples with high colloid concentrations.     

Evaluating fluorescence and ultraviolet photometry to assess dissolved organic matter removal during coagulation–flocculation

Ultraviolet absorption at 254 nm (UV₂₅₄) and peaks (A, C and T) fluorescence intensities were evaluated to assess dissolved organic carbon (DOC) removal during coagulation–flocculation. The consistency of fluorescence data was checked to ensure that no inner filter effect, quenching or enhanced intensities affected the data. The decreases in UV₂₅₄ and peak intensities were calculated in percentage terms between raw and clarified water and compared with measured DOC removal. The results indicate that peak A, peak C, peak T and UV₂₅₄ exhibit strong linear relationships (R²: 0.91, 0.89, 0.92 and 0.99, respectively) with DOC removal, implying that these parameters are useful indicators of DOC removal.     

Fate of effluent organic matter and DBP precursors in an effluent-dominated river: A case study of wastewater impact on downstream water quality

The impact of treated wastewater discharges on downstream water quality was evaluated in an effluent-dominated stream in the Southwest USA. The fate and transport of effluent organic matter (EfOM) and disinfection by-product (DBP) precursors was studied. Nitrification and biodegradation were important mechanisms. Changes in DBP formation potential along the river appeared to correlate with dissolved organic carbon (DOC) and organic nitrogen concentrations and specific ultraviolet absorbance. The mean oxidation state of carbon (MOC) decreased in value along the river. MOC decreases paralleled decreases in the biodegradability of residual DOC (i.e., lower biodegradable DOC/DOC ratio). The EfOM was biodegradable by up to 40 percent, both in the stream and in a laboratory reactor, and many DBP precursors (e.g., haloacetonitriles, certain nitrosamines) decreased in concentration. Alternatively, the DBP yields for trihalomethanes or haloacetic acids either remained the same or increased slightly, suggesting that these precursors were part of the recalcitrant organic matter (OM).     

Adsorption of dissolved natural organic matter by modified activated carbons

Adsorption of dissolved natural organic matter (DOM) by virgin and modified granular activated carbons (GACs) was studied. DOM samples were obtained from two water treatment plants before (i.e., raw water) and after coagulation/flocculation/sedimentation processes (i.e., treated water). A granular activated carbon (GAC) was modified by high temperature helium or ammonia treatment, or iron impregnation followed by high temperature ammonia treatment. Two activated carbon fibers (ACFs) were also used, with no modification, to examine the effect of carbon porosity on DOM adsorption. Size exclusion chromatography (SEC) and specific ultraviolet absorbance (SUVA(254)) were employed to characterize the DOMs before and after adsorption. Iron-impregnated (HDFe) and ammonia-treated (HDN) activated carbons showed significantly higher DOM uptakes than the virgin GAC. The enhanced DOM uptake by HDFe was due to the presence of iron species on the carbon surface. The higher uptake of HDN was attributed to the enlarged carbon pores and basic surface created during ammonia treatment. The SEC and SUVA(254) results showed no specific selectivity in the removal of different DOM components as a result of carbon modification. The removal of DOM from both raw and treated waters was negligible by ACF10, having 96% of its surface area in pores smaller than 1 nm. Small molecular weight (MW) DOM components were preferentially removed by ACF20H, having 33% of its surface area in 1--3 nm pores. DOM components with MWs larger than 1600, 2000, and 2700 Da of Charleston raw, Charleston-treated, and Spartanburg-treated waters, respectively, were excluded from the pores of ACF20H. In contrast to carbon fibers, DOM components from entire MW range were removed from waters by virgin and modified GACs.     

三维荧光技术用于给水的水质测定

采用三维荧光分析技术分类研究了原水中可溶解性有机物在传统水处理工艺中的去除过程。结果表明,三维荧光分析方法能够将原水中有机物区分成不同类型的腐殖酸和蛋白质,并揭示其在传统水处理工艺中去除效率的变化,而且三维荧光数据与COD、DOC和UV254等水质指标存在着良好的相关性。     

Production of polyhydroxyalkanoates (PHA) by activated sludge treating municipal wastewater: effect of pH,sludge retention time (SRT), and acetate concentration in influent

In this paper, the production of biodegradable plastics polyhydroxyalkanoates (PHA) by activated sludge treating municipal wastewater was investigated. The effect of three operational factors, i.e. the acetate concentration in influent, pH, and sludge retention time (SRT) were studied. Sludge acclimatized with municipal wastewater supplemented with acetate could accumulate PHA up to 30% of sludge dry weight, while sludge acclimatized with only municipal wastewater achieved 20% of sludge dry weight. It was found that activated sludge with an SRT of 3 days possessed better PHA production capability than sludge with an SRT of 10 days. Sludge acclimatized under pH 7 and 8 conditions in sequencing batch reactors (SBRs) exhibited similar PHA production capability. However, in PHA production batch experiments, pH value influenced significantly the PHA accumulation behavior of activated sludge. When pH of batch experiments was controlled at 6 or 7, a very low PHA production was observed. The production of PHA was stimulated when pH was kept at 8 or 9.     

污泥龄对活性污泥絮体中磷形态与分布的影响

以污泥龄分别为4和20 d的两组SBR反应器为研究对象,利用SMT法测定活性污泥、细菌细胞和EPS中磷的形态与分布,探讨了污泥龄对活性污泥中磷形态和分布的影响。研究结果表明,高SRT污泥的TP含量约为低SRT污泥的1.56倍,这主要是由于前者较后者有更高的OP和AP含量。高SRT污泥中细菌细胞和EPS的TP含量均高于低SRT污泥中的,且高SRT污泥中EPS的OP含量远大于低SRT污泥中的。高SRT污泥的细菌细胞和EPS分别较低SRT污泥的细菌细胞和EPS有更大的厌氧释磷量和好氧吸磷量,前者厌氧释磷和好氧吸磷主要源自其OP含量的变化,后者则主要源自其IP含量的变化;在厌氧/好氧反应过程中,污泥中EPS的IP含量改变主要源自其NAIP含量的变化。     

Seasonal variations of disinfection by-product precursors profile and their removal through surface water treatment plants

A sampling program has been undertaken to investigate the variations of disinfection by-products (DBPs) formation and nature and fate of natural organic matter (NOM) through water treatment plants in Istanbul. Specific focus has been given to the effect seasonal changes on the formation of DBPs and organic precursors levels. Water samples were collected from the three reservoirs inlet and within three major water treatment plants of Istanbul, Turkey. Changes in the dissolved organic carbon (DOC), ultraviolet absorbance at 254 nm (UV(254)), specific ultraviolet absorbance (SUVA), trihalomethane formation potential (THMFP), and haloacetic acids formation potential (HAAFP) were measured for both the treated and raw water samples. The variations of THM and HAA concentrations within treatment processes were monitored and also successfully assessed. The reactivity of the organic matter changed throughout the year with the lowest reactivity (THMFP and HAAFP) in winter, increasing in spring and reaching a maximum in fall season. This corresponded to the water being easier to treat in fall and an increase in the proportion of hydrophobic content. Understanding the seasonal changes in organic matter character and their reactivity with treatment chemicals should lead to a better optimization of the treatment processes and a more consistent water quality.     

Production of dissolved organic carbon (DOC) and trihalomethane (THM) precursor from peat soils

Water passing through the Sacramento-San Joaquin Delta contains elevated concentrations of dissolved organic carbon (DOC) and trihalomethane (THM) precursor relative to upstream waters from the Sacramento River and the San Joaquin River. Drainage from agricultural peat soils has been identified as one of the major sources of DOC and THM precursor. A series of controlled laboratory experiments were conducted to evaluate abiotic and biotic effects on the quantity and the nature of DOC and THM precursors produced from oxidized surface and reduced subsurface soils in the Delta. For abiotic effects, DOC was extracted from both soils with synthetic solutions containing a range of salinity (0-4 dS/m) and sodicity (0 to infinity ). The results showed that an increase in salinity significantly decreased the concentration of DOC in the soil-water from both soils but increased its aromaticity, as indicated by specific ultraviolet absorbance at 254 nm (SUVA). For biotic effects, peat soils were incubated over a range of temperatures (10 degrees C, 20 degrees C and 30 degrees C) and soil moisture contents (0.3-10 g water/g soil). After 8 weeks of incubation, only extracted DOC from flooded conditions and flooded and non-flooded cycles showed an increase in DOC. These findings indicate that neither salinity nor sodicity is the major factor for DOC production, but both can affect the solubility and mobility of DOC in the Delta soils. We believe wetting processes in oxidized peat soils produce significant amounts of DOC found in agricultural drainage discharged into the Delta waters.     

The role of extracellular polymeric substances on the sorption of natural organic matter

In this study, the influence of extracellular polymeric substances (EPS) composition and quantity was explored for biosorption of natural organic matter (NOM), using variants of Pseudomonas aeruginosa and Pseudomonas putida. Model EPS (sodium alginate beads) were tested and sorption capacity for NOM was also elucidated. In the absence of divalent ions, minimal NOM biosorption was observed and differences among strains were negligible. Under presence of divalent ions, biosorption of NOM was proportional to the amount of EPS secreted by P. aeruginosa variants. For sorption tests with model EPS, divalent ions also promoted biosorption of tested NOM, and total biosorption was also proportional to alginate quantity. Carboxyl group content in both alginate EPS and NOM appeared to be linked to increased biosorption via bridging with divalent ions. The alginate overproducing strain possessed more potential NOM biosorption sites, while the wild-type and alginate deficient strains possessed fewer potential binding sites. In comparison, P. putida, secreting protein-based EPS, behaved differently for NOM biosorption, due to its hydrophobicity and the structural characteristics of proteins. Hydrophobic interactions appeared to enhance the biosorption of more hydrophobic Suwannee River humic acid by P. putida, whose biosorption of more hydrophilic NOM variants was similar to the alginate deficient strain. Mechanistically, the presence of a diffuse electrical double layer will present potential energy barriers limiting biosorption; however, divalent ion concentrations in the aquatic environment will promote biosorption processes, permitting functional group interactions between EPS and NOM. Bridging between hydrophilic carboxyl groups on alginate EPS and NOM appeared to be the dominant form of biosorption, while hydrophobic interactions enhanced biosorption for protein-based EPS.     

Evaluation of UV/H2O2 treatment for the oxidation of pharmaceuticals in wastewater

Advanced oxidation treatment using low pressure UV light coupled with hydrogen peroxide (UV/H₂O₂) was evaluated for the oxidation of six pharmaceuticals in three wastewater effluents. The removal of these six pharmaceuticals (meprobamate, carbamazepine, dilantin, atenolol, primidone and trimethoprim) varied between no observed removal and >90%. The role of the water quality (i.e., alkalinity, nitrite, and specifically effluent organic matter (EfOM)) on hydroxyl radical (OH) exposure was evaluated and used to explain the differences in pharmaceutical removal between the three wastewaters. Results indicated that the efficacy of UV/H₂O₂ treatment for the removal of pharmaceuticals from wastewater was a function of not only the concentration of EfOM but also its inherent reactivity towards OH. The removal of pharmaceuticals also correlated with reductions in ultraviolet absorbance at 254 nm (UV₂₅₄), which offers utilities a surrogate to assess pharmaceutical removal efficiency during UV/H₂O₂ treatment.     

Extracellular biological organic matters in microbial fuel cell using sewage sludge as fuel

The microbial fuel cell (MFC) was applied to produce electricity using sewage sludge as a fuel. The extracellular biological organic matter (EBOM) of sludge, before and after MFC operation, was extracted using ammonium hydroxide whose hydrophobicity was characterized with XAD resin fractionation technique. Following MFC operation, the hydrophilic fraction (HPI) of EBOM was enriched (48.0%-64.5%), the hydrophobic acid (HPO-A) fraction was reduced (32.0%-14.5%), and the dissolved organic carbon (DOC) was removed by 36.8% and the sludge aromaticity decreased by 65.7%. The fluorescence tests indicated that the MFC removed the aromatic proteins-like and soluble microbial byproduct-like materials in sludge. Fourier-transform infrared (FT-IR) results showed that the aliphatic (C-H related) components, hydrocarbon and carbohydrate were easily hydrolyzed and biodegraded in the studied MFC.     

Degradation of organic matter from black shales and charcoal by the wood-rotting fungus Schizophyllum commune and release of DOC and heavy metals in the aqueous phase

We investigated the degradation of refractory organic matter (OM) by the basidiomycete fungus Schizophyllum commune to understand the release of dissolved organic compounds, heavy metals and sulfur. The investigated OM consisted of: charcoal, the short time end product of high temperature wood alteration in the absence of oxygen and composed mainly of pure OM; and black shales composed of clay minerals, quartz, sulfides and OM formed geogenically in an abiotic long-term process. In both cases, the OM fraction contains mainly polyaromatic hydrocarbons. We investigated the degradation of these fractions by a wood-rotting basidiomycete, which is able to produce exoenzymes like peroxidases and laccases. These enzymes can perform radical reactions to oxidize OM (like lignin) and therefore hypothetically are able to degrade OM from charcoal and/or low grade metamorphic black shales. Release of new components into dissolved organic carbon (DOC) could be detected in both cases. The attack on OM in the case of black shales coincided with the release of the heavy metals Fe, Mn and Ni. By following sulfur concentrations throughout the experiment, it was shown that heavy metal release is not due to pyrite oxidation. Ground black shale and charcoal samples were inoculated with S. commune in a diluted minimal medium containing aspartic acid and glucose. The aqueous and solid phases were sampled after 1, 7, 28 and 84 days. DOC was measured as non purgeable carbon and characterized by size exclusion chromatography and UV detection. Carbon concentrations of the solid phase were determined by element analyses. After initial decrease of the DOC concentrations due to the degradation of the carbon source provided with the medium, DOC increased up to 80 mg/l after 84 days. Carbon decreased in the solid fraction confirming that this carbon was released as DOC by the fungus. The newly generated DOC formed larger agglomerations than the DOC of the growth medium. The investigation proved that the degradation of persistent carbon sources, such as charcoal and black shale, is accelerated by fungal activity. Consequently, the associated release of heavy metals is also accelerated by the fungus. Main products of the biological degradation processes were organic heavy metal complexes which can enter the environment.