Systematic assessment of the ecotoxicological effects and mechanisms of biochar-derived dissolved organic matter (DOM) on the earthworm Eisenia fetida.

Biochar-derived dissolved organic matter (DOM) contains toxic substances that are first released into the soil after biochar application. However, the ecological risks of biochar-derived DOM on soil invertebrate earthworms are unclear. Therefore, this study investigated the ecological risks and toxic mechanisms of sewage sludge biochar (SSB)-derived DOM on the earthworm Eisenia fetida (E. fetida) via microcosm experiments. DOM exposure induced earthworm death, growth inhibition, and cocoon decline. Moreover, DOM, especially the 10% DOM300 (derived from SSB prepared at 300 °C) treatments, disrupted the antioxidant defense response and lysosomal stability in earthworms. Integrated biomarker response v2 (IBRv2) analysis was performed to assess the comprehensive toxicity of DOM in E. fetida, and the results revealed that DOM300 might exert more hazardous effects on earthworms than DOM500 (prepared at 500 °C) and DOM700 (prepared at 700 °C), as revealed by increases in the IBRv2 value of 3.48-18.21. Transcriptome analysis revealed that 10% DOM300 exposure significantly disrupted carbohydrate and protein digestion and absorption and induced endocrine disorder. Interestingly, 10% DOM300 exposure also significantly downregulated the expression of genes involved in signaling pathways, e.g., the P13K-AKT, cGMP-PKG, and ErbB signaling pathways, which are related to cell growth, survival, and metabolism, suggesting that DOM300 might induce neurotoxicity in E. fetida. Altogether, these results may contribute to a better understanding of the toxicity and defense mechanisms of biochar-derived DOM on earthworms, especially during long-term applications, and thus provide guidelines for using biochar as a soil amendment.

Investigation of dissolved organic matter's influence on the toxicity of cadmium to the cyanobacterium Microcystis aeruginosa by biochemical and molecular assays.

Rapid economic development has increased the accumulation of dissolved organic matter (DOM) and heavy metals in aquatic environments. In addition, Microcystis aeruginosa can cause the outbreak of cyanobacteria bloom and can produce microcystin, which poses a threat to human water safety. Therefore, this study analyzed the biochemical and molecular assays of DOM (0, 1, 3, 5, 8, 10 mg C L-1) extracted from four different sources on the toxicity of cadmium (Cd) to M. aeruginosa. The results showed that the addition of different concentrations of DOM from sediment, biochar, and humic acid alleviated the toxicity of Cd to M. aeruginosa. But the addition of rice hulls DOM at high concentrations (8 and 10 mg L-1) significantly reduced the normal growth and metabolic activities of M. aeruginosa. DOM from four different sources promoted the expression level of microcystin-related gene mcyA and the production of microcystin-leucine-arginine (MC-LR), and mcyA was positively correlated with MC-LR. DOM from biochar, sediment, and humic acid were able to bind Cd through complexation. The results will help to understand the toxic effects of heavy metals on toxic-producing cyanobacteria in the presence of DOM, and provide certain reference for the evaluation of water environmental health.

Potential linkage between WWTPs-river-integrated area pollution risk assessment and dissolved organic matter spectral index.

The direct discharge of wastewater can cause severe damage to the water environment of the surface water. However, the influence of dissolved organic matter (DOM) present in wastewater on the allocation of DOM, nitrogen (N), and phosphorus (P) in rivers remains largely unexplored. Addressing the urgent need to monitor areas affected by direct wastewater discharge in a long-term and systematic manner is crucial. In this paper, the DOM of overlying water and sediment in the WWTPs-river-integrated area was characterized by ultraviolet-visible absorption spectroscopy (UV-vis), three-dimensional excitation-emission matrix combined with parallel factor (PARAFAC) method. The effects of WWTPs on receiving waters were investigated, and the potential link between DOM and N, P pollution was explored. The pollution risk was fitted and predicted using a spectral index. The results indicate that the improved water quality index (IWQI) is more suitable for the WWTPs-river integration zone. The DOM fraction in this region is dominated by humic-like matter, which is mainly influenced by WWTPs drainage as well as microbial activities. The DOM fractions in sediment and overlying water were extremely similar, but fluorescence intensity possessed more significant spatial differences. The increase in humic-like matter facilitates the production and preservation of P and also inhibits nitrification, thus affecting the N cycle. There is a significant correlation between DOM fraction, fluorescence index, and N, P. Fluorescence index (FI) fitting of overlying water DOM predicted IWQI and trophic level index, and a(254) fitting of sediment DOM predicted nitrogen and phosphorus pollution risk (FF) with good results. These results contribute to a better understanding of the impact of WWTPs on receiving waters and the potential link between DOM and N and P pollution and provide new ideas for monitoring the water environment in highly polluted areas.

Field evidences of fluorescent dissolved organic matter (FDOM) as potential fingerprints for agricultural and urban sources in river environment.

Field evidences of the fluorescence differences between agricultural and urban river reaches are still lack. In this study, the middle reaches of Danhe River (DH) and Mihe River (MH) in Shouguang, China, were designed as agricultural and urban river reaches, respectively, to compare the the fluorescence differences in disparate river reaches using excitation-emission matrix coupled with parallel factor analysis (EEM-PARAFAC). Three fluorescence components were identified. C1 (Ex/Em=230,255,295 nm/420 nm) was categorized as humic-like fluorophores, C2 (Ex/Em=230,275 nm/330 nm) was recognized as tryptophan-like substances, and C3 (Ex/Em=215 nm/290 nm) was noted as tyrosine-like and phenylalanine-like compounds. The results showed that the FDOM posed significant differences between agricultural and urban river reaches (P < 0.001). The monitoring sites in DH were rich in C2 (1.90 ± 0.62 Raman Unit (RU), mean ± standard deviation), and the monitoring sites in MH were rich in C3 (1.32 ± 0.51 RU). Redundancy analysis revealed that C2 could be regarded as a fluorescence indicator of agricultural sewage in river environment, while C3 was recognized as a fluorescence indicator of domestic sewage in river environment. In conclusion, this study provided field evidences of FDOM as potential fingerprints for agricultural and urban sources in river environment.

Estimation and potential ecological risk assessment of multiphase PAEs in mangrove wetlands in Dongzhai Harbor, Hainan.

With the application of plastic products, phthalates now widely occur in various environmental media. A large number of ecological risk assessment experiments have only been carried out on a single medium such as water or sediment. There are few reports of ecological risk assessments based on the phase states of phthalic acid esters (PAEs) such as the free dissolved state and the dissolved organic carbon (DOC) adsorption state. In this study, the concentrations of the free dissolved state, the DOC adsorption state, and the easily released PAEs in the sediments, as well as the dissolved organic carbon release potential and their influencing factors were calculated in the Dongzhaigang water body. The potential ecological risks posed by state-of-the-art PAEs were investigated. The average concentration of six freely dissolved PAEs in water was 0.542 (0.226-1.115) µg/L, accounting for 76.3 % of the total PAEs. The PAEs with the highest concentrations in the free dissolved state were di-n-butyl phthalate (DBP, 0.383 µg/L), followed by Di(2-ethylhexyl) phthalate (DEHP, 0.094 µg/L). The average concentration of all six PAEs (∑6PAEs) adsorbed by the DOC in the water was 0.172 µg/L, accounting for 23.74 % of all of the PAEs. The DOC-adsorbed DEHP (0.148 µg/L) accounted for about 86 % of the six adsorbed PAEs. Sediment organic carbon may affect the release potential of the DOC through changing the soluble organic carbon concentration. Most types of PAEs in water posed low risk to organisms. However, DBP posed low and medium risk to algae and crustaceans, and medium risk to fish. Medium or high risk of DEHP to algae, crustaceans and fish was observed. The high ecological risk of PAEs related to sediments were only found at S13 and S14. Generally, the potential ecological risk of PAEs in sediment was more stable than that in water bodies.

Comprehensive assessment of dissolved organic matter processing in the Amazon River and its major tributaries revealed by positive and negative electrospray mass spectrometry and NMR spectroscopy.

Rivers are natural biogeochemical systems shaping the fates of dissolved organic matter (DOM) from leaving soils to reaching the oceans. This study focuses on Amazon basin DOM processing employing negative and positive electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI[±] FT-ICR MS) and nuclear magnetic resonance spectroscopy (NMR) to reveal effects of major processes on the compositional space and structural characteristics of black, white and clear water systems. These include non-conservative mixing at the confluences of (1) Solimões and the Negro River, (2) the Amazon River and the Madeira River, and (3) in-stream processing of Amazon River DOM between the Madeira River and the Tapajós River. The Negro River (black water) supplies more highly oxygenated and high molecular weight compounds, whereas the Solimões and Madeira Rivers (white water) contribute more CHNO and CHOS molecules to the Amazon River main stem. Aliphatic CHO and abundant CHNO compounds prevail in Tapajos River DOM (clear water), likely originating from primary production. Sorption onto particles and heterotrophic microbial degradation are probably the principal mechanisms for the observed changes in DOM composition in the Amazon River and its tributaries.

Assessment of agricultural waste biochars for remediation of degraded water-soil environment: Dissolved organic carbon release and immobilization of impurities in one- or two-adsorbate systems.

This paper presents a method of agricultural waste management - the production of two biochars (BC) from potato and raspberry stems. It defines the potential of these materials for remediation of degraded water and soil environments. The performed study included analyses of BC physicochemistry, dissolved organic carbon (DOC) release and ability to immobilize copper (Cu), tetracycline (TC) and carboxin (CB) in one- and two-adsorbate systems. The BCs were obtained with pyrolysis at 600 °C for 30 min in a nitrogen atmosphere. Their DOC was predominantly constituted of substances with large molecular weights and high aromaticity, meaning that both BCs can be safely applied as soil additives. Potato-biochar (P-BC) had a more developed surface than raspberry-biochar (R-BC). The specific surface area (SBET) of P-BC was 122 m2/g, whilst of R-BC was 87 m2/g. As a result, the efficiency of impurity adsorption in the one-adsorbate systems was higher for P-BC (61.75% for Cu, 73.84% for TC, and 54.43% for CB). In the two-adsorbate systems, organic impurities improved the immobilization of heavy metal ions on BCs. The efficiency of Cu adsorption on P-BC when TC was present was 88.29%. Desorption of Cu from BC was highest using HCl, whilst that of TC and CB was highest using NaOH. Maximum desorption was observed in a two-adsorbate system with TC + CB (up to 63.6% for TC). These results confirmed that potato and raspberry stems can be used to produce highly effective BCs with large application potential, especially for remediation of degraded soils and polluted waters.

Water quality assessment in mosquito breeding habitats based on dissolved organic matter and chlorophyll measurements by laser-induced fluorescence spectroscopy.

Rapid urbanization and its associated pollution can affect water quality in mosquito breeding habitats and, as a result, the ecology and control of mosquito vectors. To understand the effects of pollution on mosquito vectors, an accurate assessment of water quality in breeding habitats is needed. Presently, water quality assessment of mosquito breeding habitats is usually based on the measurement of individual physicochemical parameters. However, several parameters are sometimes difficult to interpret or may not give a clear picture of the overall water quality of the breeding habitats, especially when the pollutants are in complex mixtures. This study employed the use of Laser-Induced Fluorescence (LIF) spectroscopy to assess water quality in breeding habitats of Anopheles, Aedes, and Culex mosquitoes in urban areas in Cape Coast, Ghana. The LIF spectra, using a 445-nm diode laser, were measured from field-collected water samples in the laboratory. The LIF spectra showed the presence of dissolved organic matter (DOM) and chlorophyll in the breeding habitats. The DOM and chlorophyll fluorescence signals were normalised by the Raman vibrational signals to determine water quality in each habitat. The overall water quality was better in Aedes breeding habitats than in Anopheles and Culex breeding habitats. The poor water quality in Anopheles and Culex breeding habitats was due to the presence of high fulvic acid and chlorophyll content, which often reflect pollutants from anthropogenic sources. Anopheles and Aedes habitats were made up of mainly An. coluzzii and Ae. aegypti respectively while Culex species were identified to genus level. The results add up to the growing concern about the breeding of Anopheles in polluted habitats. The study demonstrated for the first time the ability of LIF spectroscopy to assess water quality in mosquito breeding habitats.

Comparison of organic matter (OM) pools in water, suspended particulate matter, and sediments in eutrophic Lake Taihu, China: Implication for dissolved OM tracking, assessment, and management.

Suspended particulate matter (SPM) and sediments are important sources of dissolved organic matter (DOM) in lake water. However, studies on what extent and how both sources affect DOM composition are lacking, which hampers DOM management. Herein, DOM, SPM-extracted particulate organic matter (POM), and sediment-extracted organic matter (SOM) were characterized and compared in terms of absorption spectral properties and chemical composition in Lake Taihu, a large cyanobacterial bloom-affected shallow lake. A statistical method was proposed to quantify the similarity of organic matter (OM) in the different states and to evaluate the potential effects of SPM and sediments on DOM. Results showed that POM and DOM were mainly composed of small-molecular-size and low-humified organic components (i.e., 27 %-38 % tryptophan-like and ~30 % protein-like substances), and most of them were derived from autochthonous sources. While tyrosine-like (57 %) and humic-like (27 %) substances were dominant in SOM. The OM similarity between POM and DOM was approximately 1.5 times higher than that between SOM and DOM, indicating the greater effect of SPM than sediments on DOM composition. High pH and low nitrogen (e.g., nitrate and ammonia) were positively correlated to the OM similarity between POM and DOM. Further, the findings indicated that nitrogen limitation enhanced the OM exchange between POM and DOM by promoting the production of extracellular polymeric substances (EPS) in cyanobacterial aggregates. The obtained findings highlighted the importance of SPM in shaping the DOM composition relative to sediments and facilitating the DOM management in bloom-affected lakes.

Assessment of potential biotoxicity induced by biochar-derived dissolved organic matters to biological fermentative H2 production.

Biochar is a widely used antecedent for improving bio­hydrogen production. However, little is known about the impact of biochar-derived dissolved organic matter (DOM) on the performance of fermentative bio-H2 production. Herein, we evaluated the impact of biochar-derived DOM on the fermentation performance of hydrogen-producing microflora. The pyrolysis temperature of biochar affected the DOM composition, with lower pyrolysis temperatures showing more serious inhibition on H2 accumulation. When biochar was pyrolyzed at 500 °C, DOM prolonged the fermentation period and decreased H2 production from 1330.41 mL L-1 to 1177.05 mL L-1 compared to the control group. The xylose utilization in mixed substrate decreased from 29.72% to 26.41%, which is not favorable for practical applications where lignocellulosic biomass is used as a substrate. Otherwise, DOM caused a 6% reduction in microbial biomass accumulation and less soluble metabolites formation. The potential mechanism of DOM inhibiting bio­hydrogen production was verified by identifying an increase in reactive oxygen species (ROS) level (178.2%) and the microbial community shifted to containing fewer hydrogen-producing strains. The finding prompts a more precise design of biochar applications in fermentation systems to alleviate the potential hazards and maximum the fermentation performance, not limited to fermentative hydrogen production system.

"Humic substances" measurement in sludge dissolved organic matter: A critical assessment of current methods.

The role of humic substances (HS) during sludge treatment has been the focus in recent years. Quantification of HS in sludge dissolved organic matter (DOM) and the chemical and structural characterization of HS data are the prerequisite for understanding their role during different sludge treatment processes. Currently, a number of published articles inadequately acknowledge fundamental principles of analysis methods both in terms of experimental approach and data analysis. Therefore, a more comprehensive and detailed description of the experimental methods and the data analysis are needed. In this study, the current used methods for HS quantification in DOM of sludge had been tested for different calibration and sludge DOM samples. The results indicated that the current methods showed overestimated and contradictory results for HS quantification in sludge DOM. To be specific, using the modified Lowry method, different values were obtained depending on the humic acids used for calibration, and false negative results were observed for some sludge samples. By using the relative amount of HS (based on dissolved organic carbon (DOC)) to total sludge DOM (based on DOC), variations among the results of different analysis methods for the same sample were high. According to the calculated Bray-Curtis dissimilarity indexes, the results for HS quantification obtained by three-dimensional excitation emission matrix (3D-EEM), either with spectra analysis methods by peak picking, fluorescence region integration (both region volume and area integration), or PARAllel FACtor analysis showed higher degrees of dissimilarity to those quantified by size exclusion liquid chromatography or XAD-8 method. The selection of fluorescence regions for HS seemed to be the determining factor for overestimation obtained by the 3D-EEM technique. In future work, strategies, like a consistent terminology of HS, the use of an internal standard sample, and the related standardized operation for HS quantification in sludge DOM need to be established.

Assessment of leachable and persistent dissolved organic carbon in sludges and biosolids from municipal wastewater treatment plants.

Environmental regulation of organic pollutants has not kept pace with the growth in the number and diversity of legacy and emerging organic substances now in use. Simpler and cheaper tools and methodologies are needed to quickly assess the organic pollutant risks in waste materials applied to land such as municipal wastewater treatment sludges and biosolids. This study attempts to provide these, using an approach that consists of chemical leaching and analysis of dissolved organic carbon and determination of its biodegradability by measuring persistent dissolved organic carbon. Primary and secondary sludges, dewatered sludge cake, and anaerobically and thermally treated biosolids obtained from various types of municipal wastewater treatment plants were used in the study. The study found little variability in the levels of dissolved organic carbon leached from primary sludges obtained from different municipal wastewater treatment plants but found significant differences for secondary sludges based on levels of nitrification at the municipal wastewater treatment plants. As predicted treated biosolids leached less dissolved organic carbon than untreated dry sludges but had relatively higher proportions of persistent or poorly biodegradable dissolved organic carbon. Across all tested sludges and biosolids persistent dissolved organic carbon ranged from 14 to 39%, with biosolids that have undergone anaerobic digestion and thermal treatment more likely to contain greater relative proportion of persistent dissolved organic carbon than untreated sludges. The approach presented in this study will be useful in assessing the effectiveness of current and widely employed sludge treatment methods in reducing persistent organic pollutants in biosolids disposed on land.

Exploring Spatially Explicit Changes in Carbon Budgets of Global River Basins during the 20th Century.

Rivers play an important role in the global carbon (C) cycle. However, it remains unknown how long-term river C fluxes change because of climate, land-use, and other environmental changes. Here, we investigated the spatiotemporal variations in global freshwater C cycling in the 20th century using the mechanistic IMAGE-Dynamic Global Nutrient Model extended with the Dynamic In-Stream Chemistry Carbon module (DISC-CARBON) that couples river basin hydrology, environmental conditions, and C delivery with C flows from headwaters to mouths. The results show heterogeneous spatial distribution of dissolved inorganic carbon (DIC) concentrations in global inland waters with the lowest concentrations in the tropics and highest concentrations in the Arctic and semiarid and arid regions. Dissolved organic carbon (DOC) concentrations are less than 10 mg C/L in most global inland waters and are generally high in high-latitude basins. Increasing global C inputs, burial, and CO2 emissions reported in the literature are confirmed by DISC-CARBON. Global river C export to oceans has been stable around 0.9 Pg yr-1. The long-term changes and spatial patterns of concentrations and fluxes of different C forms in the global river network unfold the combined influence of the lithology, climate, and hydrology of river basins, terrestrial and biological C sources, in-stream C transformations, and human interferences such as damming.