Long-term Incubation Experiments Research Articles

Wheat Straw Biochar as a Specific Sorbent of Cobalt in Soil.

There is an urgent need to search for new sorbents of pollutants presently delivered to the environment. Recently biochar has received much attention as a low-cost, highly effective heavy metal adsorbent. Biochar has been identified as an efficient material for cobalt (Co) immobilization from waters; however, little is known about the role of Co immobilization in soil. Hence, in this study, a batch experiment and a long-term incubation experiment with biochar application to multi-contaminated soil with distinct properties (sand, loam) were conducted to provide a brief explanation of the potential mechanisms of Co (II) sorption on wheat straw biochar and to describe additional processes that modify material efficiency for metal sorption in soil. The soil treatments with 5% (v/w) wheat straw biochar proved to be efficient in reducing Co mobility and bioavailability. The mechanism of these processes could be related to direct and indirect effects of biochar incorporation into soil. The FT-IR analysis confirmed that hydroxyl and carboxyl groups present on the biochar surface played a dominant role in Co (II) surface complexation. The combined effect of pH, metal complexation capacity, and the presence of Fe and Mn oxides added to wheat straw biochar resulted in an effective reduction of soluble Co (II), showing high efficiency of this material for cobalt sorption in contaminated soils.

Zeolite-supported nanoscale zero-valent iron for immobilization of cadmium, lead, and arsenic in farmland soils: Encapsulation mechanisms and indigenous microbial responses

Zeolite-supported nanoscale zero-valent iron (Z-NZVI) has great potential for metal(loid) removal, but its encapsulation mechanisms and ecological risks in real soil systems are not completely clear. We conducted long-term incubation experiments to gain new insights into the interactions between metal(loid)s (Cd, Pb, As) and Z-NZVI in naturally contaminated farmland soils, as well as the alteration of indigenous bacterial communities during soil remediation. With the pH-adjusting and adsorption capacities, 30 g kg−1 Z-NZVI amendment significantly decreased the available metal(loid) concentrations by 10.2–96.8% and transformed them into strongly-bound fractions in acidic and alkaline soils after 180 d. An innovative magnetic separation of Z-NZVI from soils followed by XRD and XPS characterizations revealed that B-type ternary complexation, heterogeneous coprecipitation, and/or concurrent redox reactions of metal(loid)s, especially the formation of Cd3(AsO4)2, PbFe2(AsO4)2(OH)2, and As0, occurred only under specific soil conditions. Sequencing of 16S rDNA using Illumina MiSeq platform indicated that temporary shifts in iron-resistant/sensitive, pH-sensitive, denitrifying, and metal-resistant bacteria after Z-NZVI addition were ultimately eliminated because soil characteristics drove the re-establishment of indigenous bacterial community. Meanwhile, Z-NZVI recovered the basic activities of bacterial DNA replication and denitrification functions in soils. These results confirm that Z-NZVI is promising for the long-term remediation of metal(loid)s contaminated farmland soil without significant ecotoxicity.

Comprehensive Evaluation of the Biological Properties of Surface-Modified Titanium Alloy Implants.

An increasing interest in the fabrication of implants made of titanium and its alloys results from their capacity to be integrated into the bone system. This integration is facilitated by different modifications of the implant surface. Here, we assessed the bioactivity of amorphous titania nanoporous and nanotubular coatings (TNTs), produced by electrochemical oxidation of Ti6Al4V orthopedic implants’ surface. The chemical composition and microstructure of TNT layers was analyzed by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). To increase their antimicrobial activity, TNT coatings were enriched with silver nanoparticles (AgNPs) with the chemical vapor deposition (CVD) method and tested against various bacterial and fungal strains for their ability to form a biofilm. The biointegrity and anti-inflammatory properties of these layers were assessed with the use of fibroblast, osteoblast, and macrophage cell lines. To assess and exclude potential genotoxicity issues of the fabricated systems, a mutation reversal test was performed (Ames Assay MPF, OECD TG 471), showing that none of the TNT coatings released mutagenic substances in long-term incubation experiments. The thorough analysis performed in this study indicates that the TNT5 and TNT5/AgNPs coatings (TNT5—the layer obtained upon applying a 5 V potential) present the most suitable physicochemical and biological properties for their potential use in the fabrication of implants for orthopedics. For this reason, their mechanical properties were measured to obtain full system characteristics.

Effects of low pH and feeding on calcification rates of the cold-water coral Desmophyllum dianthus.

Cold-Water Corals (CWCs), and most marine calcifiers, are especially threatened by ocean acidification (OA) and the decrease in the carbonate saturation state of seawater. The vulnerability of these organisms, however, also involves other global stressors like warming, deoxygenation or changes in sea surface productivity and, hence, food supply via the downward transport of organic matter to the deep ocean. This study examined the response of the CWC Desmophyllum dianthus to low pH under different feeding regimes through a long-term incubation experiment. For this experiment, 152 polyps were incubated at pH 8.1, 7.8, 7.5 and 7.2 and two feeding regimes for 14 months. Mean calcification rates over the entire duration of the experiment ranged between −0.3 and 0.3 mg CaCO3 g−1d−1. Polyps incubated at pH 7.2 were the most affected and 30% mortality was observed in this treatment. In addition, many of the surviving polyps at pH 7.2 showed negative calcification rates indicating that, in the long term, CWCs may have difficulty thriving in such aragonite undersaturated waters. The feeding regime had a significant effect on skeletal growth of corals, with high feeding frequency resulting in more positive and variable calcification rates. This was especially evident in corals reared at pH 7.5 (ΩA = 0.8) compared to the low frequency feeding treatment. Early life-stages, which are essential for the recruitment and maintenance of coral communities and their associated biodiversity, were revealed to be at highest risk. Overall, this study demonstrates the vulnerability of D. dianthus corals to low pH and low food availability. Future projected pH decreases and related changes in zooplankton communities may potentially compromise the viability of CWC populations.

Methane formation in tropical reservoirs predicted from sediment age and nitrogen

Freshwater reservoirs, in particular tropical ones, are an important source of methane (CH4) to the atmosphere, but current estimates are uncertain. The CH4 emitted from reservoirs is microbially produced in their sediments, but at present, the rate of CH4 formation in reservoir sediments cannot be predicted from sediment characteristics, limiting our understanding of reservoir CH4 emission. Here we show through a long-term incubation experiment that the CH4 formation rate in sediments of widely different tropical reservoirs can be predicted from sediment age and total nitrogen concentration. CH4 formation occurs predominantly in sediment layers younger than 6–12 years and beyond these layers sediment organic carbon may be considered effectively buried. Hence mitigating reservoir CH4 emission via improving nutrient management and thus reducing organic matter supply to sediments is within reach. Our model of sediment CH4 formation represents a first step towards constraining reservoir CH4 emission from sediment characteristics.

HPLC-SEC-FTIR characterization of the dissolved organic matter produced by the microbial carbon pump

The microbial carbon pump (MCP) concept regroups different processes that contribute to the formation of refractory dissolved organic matter (DOM) from labile substrates. In this study, long-term (1 yr) incubation experiments in fresh- and sea-waters were done with glucose as the only source of carbon for microorganisms. Bulk carbon, glucose and amino acid enantiomers analyses confirmed that glucose was transformed into microbial biomass and complex non-labile DOM. Dissolved organic carbon concentrations decreased during the first four months and then remained constant at ~20% of the initial level. After one year, the microbial DOM and DOM from natural waters were concentrated by evaporation and a low volume solid-phase extraction (SPE) that resulted in a very high (70 to 85%) extraction efficiency. These SPE-DOM samples were characterized by size-exclusion chromatography (HPLC-SEC) coupled with Fourier transform infrared spectroscopy (FTIR). These are the first HPLC-SEC-FTIR analyses of microbial DOM and of such high proportions of natural DOM. Results revealed that microbial DOM showed all the FTIR absorption bands seen in the DOM from natural waters. However, amino acids, carbohydrates, and aliphatic CH were more abundant in the microbial DOM, whereas phenols and esters were more visible in DOM from natural waters. It was difficult to identify consistent (in all samples) compositional trends according to molecular weight (MW). Cluster analyses showed that 72% of the variability in the relative absorbance for all the bands was explained by the origin and the type of the DOM extracts. The microbial DOM from freshwater had the most unique bulk composition while the microbial DOM from seawater was more similar to the DOM from natural waters. The DOM from natural fresh- and sea-waters exhibited the most similar composition when all the bands and MW are considered. The lack of consistent trends in the composition of the samples having the same origin (e.g., the two microbial DOM or the two freshwater DOM) shows the high heterogeneity and complexity of DOM, including the microbial non-labile DOM produced by the MCP. This suggests that the MCP contributes to the heterogeneity and complexity of the DOM found in natural waters.

How do sand addition, soil moisture and nutrient status influence greenhouse gas fluxes from drained organic soils?

Drainage turns peatlands from natural carbon sinks into hotspots of greenhouse gas (GHG) emissions from soils due to alterations in hydrological and biogeochemical processes. As a consequence of drainage-induced mineralisation and anthropogenic sand addition, large areas of former peatlands under agricultural use have soil organic carbon (SOC) contents at the boundary between mineral and organic soils. Previous research has shown that the variability of GHG emissions increases with anthropogenic disturbance. However, how and whether sand addition affects GHG emissions remains a controversial issue. The aim of this long-term incubation experiment was to assess the influence of hydrological and biogeochemical soil properties on emissions of carbon dioxide (CO2), nitrous oxide (N2O) and methane (CH4). Strongly degraded peat with sand addition (peat-sand mixtures) and without sand addition (earthified peat) was systematically compared under different moisture conditions for fen and bog peat. Soil columns originating from both the topsoil and the subsoil of ten different peatlands under grassland use were investigated. Over a period of six months the almost saturated soil columns were drained stepwise via suction to −300 hPa. The CO2 fluxes were lowest at water-saturated and dry soil moisture conditions, resulting in a parabolic dependence of CO2 fluxes on the water-filled pore space (WFPS) peaking at 56–92% WFPS. The highest N2O fluxes were found at between 73 and 95% WFPS. Maximum CO2 fluxes were highest from topsoils, ranging from 21 to 77 mg C m−2 h−1, while the maximum CO2 fluxes from subsoils ranged from 3 to 14 mg C m−2 h−1. No systematic influence of peat type or sand addition on GHG emissions was found in topsoils, but CO2 fluxes from subsoils below peat-sand mixtures were higher than from subsoils below earthified peat. Maximum N2O fluxes were highly variable between sites and ranged from 18.5 to 234.9 and from 0.2 to 22.9 μg N m−2 h−1 for topsoils and subsoils, respectively. CH4 fluxes were negligible even under water-saturated conditions. The highest GHG emissions occurred at a WFPS that relates – under equilibrium conditions – to a water table of 20–60 cm below the surface in the field. High maximum CO2 and N2O fluxes were linked to high densities of plant-available phosphorus and potassium. The results of this study highlight that nutrient status plays a more important role in GHG emissions than peat type or sand addition, and do not support the idea of peat-sand mixtures as a mitigation option for GHG emissions.

Wheat straw biochar reduces environmental cadmium bioavailability

Cadmium contamination in waters and soils can lead to food chain accumulation and ultimately deterioration in human health; means for reducing bioavailable Cd are desperately required, and biochars may play a role. Long-term (240 d) lab incubation experiments were utilized to explain wheat straw-derived biochar effects on Cd sorption and decreasing Cd bioavailability in soils and solutions (0, 5, and 15% biochar as wt:wt or wt:vol, respectively), and to identify Cd forms present using both the European Community Bureau of Reference (BCR) chemical sequential extraction procedure and synchrotron-based X-ray absorption spectroscopy (XAS). Biochar Cd removal was up to ~90% from Cd-containing solutions and contaminated soil as compared to the control. Based on the wet chemical sequential extraction procedure in conjunction with XAS, biochar application promoted the formation of (oxy)hydroxide, carbonate, and organically bound Cd phases. As a material, biochar may be promoted as a tool for reducing and removing bioavailable Cd from contaminated waters and soils. Thus, biochar may play a role in reducing Cd bioaccumulation, trophic transfer, and improving environmental quality and human health.

Performance of physical and chemical methods in the co-reduction of internal phosphorus and nitrogen loading from the sediment of a black odorous river

The continuous release of nutrients from sediment is a major barrier to the remediation of black odorous rivers. This study used a long-term laboratory incubation experiment to investigate the effectiveness of sediment dredging, intermittent aeration, and in situ inactivation with modified clays to reduce the internal loading of sediment from a seriously polluted river. The results indicated that intermittent aeration and in situ inactivation were effective in reducing the TN and NH4+ concentrations in the water column. However, sediment dredging did not consistently reduce the TN and NH4+ concentrations in the water column. In contrast, the three methods were all effective in controlling the TP and PO43− concentrations in the water column. Except for dredging, >30% of NH4+ and 40% of PO43− fluxes from sediment were reduced when compared with a control sample after 120 days of remediation. Dredging induced a significant release of NH4+ from sediment. Dredging and aeration made nearly no change to the amount of extractable nitrogen in the sediment. However, inactivation may increase sediment-extractable ammonium in deep sediment layers with time due to vertical transportation of clay by intensive bioturbation. Dredging is the most effective way to reduce surface mobile phosphorus over time while the transported clays can reduce a large percentage of the mobile phosphorus in deeper sediment. The relative abundance of Nitrospira in the surface sediment increased significantly with each remediation measure, creating favorable conditions for the reduction of the ammonium released from sediment. Altogether, the results of this study indicated that clay inactivation is the best method for controlling the internal loading of both phosphorus and nitrogen in seriously polluted river sediment.

Gas production from dredged sediment

The anaerobic degradation of sediment organic matter leads to considerable gas production in constructions made from sediments and in landfills where contaminated sediments are disposed of, inducing problems with the mechanical stability of constructions or necessitating extraction and treatment of gas. However, little is known about the magnitude of gas generation from dredged sediment, hence validated input parameters for gas production modelling are missing. On the occasion of drillings performed for the installation of inclinometers on a mono-landfill for contaminated dredged sediment, eleven waste layers of known were sampled. Samples were analysed for gas generation in a long-term laboratory incubation experiment carried out for 757 days. It was found that the residual gas potential of the deposited dredged material ranged between 2 and 12 m3 MgDW−1, relating to 3–11% of the organic matter being degraded. Correlation analyses with material properties suggest a strong role of nitrogen, either directly or as indicative parameter, with the gas potential increasing with total nitrogen content and the share of degradable carbon decreasing with increasing TOC/TN ratio. The by far greatest share of organic matter was bound in the heavy density fraction >1.4 g cm−3, suggesting that the readily available light organic matter pool had already been depleted during pre-treatment of the dredged sediment in dewatering fields and the subsequent years of landfilling. Consequently, the correlation of the remaining gas potential with heavy fraction nitrogen was even stronger than for bulk nitrogen. The gas potential as revealed from the long-term test correlated well with short-term values, but outreached the commonly applied potential measured for 21 days by the factor of four. The data improve the state of knowledge on gas production from the large mineral waste stream of dredged material and serve to improve gas production modelling for these types of wastes. The strong correlation of gas potential to TN suggests that TN may serve as a proxy to estimate total gas potential.

Mature biofilm communities on synthetic polymers in seawater - Specific or general?

To understand the ecological impacts of the “Plastisphere”, those microbes need to be identified that preferentially colonize and interact with synthetic polymer surfaces, as opposed to general surface colonizers. It was hypothesized that the microbial biofilm composition varies distinctly between different substrates. A long-term incubation experiment was conducted (15month) with nine different synthetic polymer films as substrate as well as glass using a natural seawater flow-through system. To identify colonizing microorganisms, 16S and 18SrRNA gene tag sequencing was performed. The microbial biofilms of these diverse artificial surfaces were visualized via scanning electron microscopy. Biofilm communities attached to synthetic polymers are distinct from glass associated biofilms; apparently a more general marine biofilm core community serves as shared core among all synthetic polymers rather than a specific synthetic polymer community. Nevertheless, characteristic and discriminatory taxa of significantly different biofilm communities were identified, indicating their specificity to a given substrate.

Alteration of organic matter during remediation of acid sulfate soils

When acid sulfate soils with hypersulfidic material dry, oxidation of pyrite can cause strong acidification due to formation of sulfuric (pH < 4) material. Re-saturation of acid sulfate soils containing sulfuric material can lead to re-formation of pyrite and pH increase through activity of sulfate reducing bacteria, which require available organic carbon (OC). In the Lower River Murray region in Australia, a clayey acid sulfate soil had acidified during the severe “Millennium” drought between 2007 and early 2010. We investigated why it has not recovered for over a decade after being reflooded. We hypothesized that the low quality and availability of OC limits the activity of sulfate reducing bacteria.A long-term anoxic incubation experiment was conducted to test if OC additions can help to overcome OC limitation. Small-scale incubation vessels were used, allowing investigating general biochemical phenomena under controlled laboratory conditions. Pre-incubated acid sulfate soil with sulfuric material (approx. pH 3.5) was submerged and pre-adjusted to pH 5.0. We used different rates of wheat straw and cattle manure application to test different organic matter quantities and qualities. Both substrates were added in two portions, at the beginning of the experiment and after 190 days. With every addition, we added two different amounts of organic matter (2 mg g−1 soil and 9 mg g−1 soil), equivalent to approx. 10% and 50% of the native soil OC content. A control treatment without OC addition was also included. CO2 production as well as redox and pH values were monitored weekly over a year. At the start and the end of incubation, we determined OC concentrations and the proportion of available, non mineral-associated OC. OC composition was analyzed by solid-state 13C NMR spectroscopy to assess its chemical degradation.The pH values increased rapidly in treatments with high OC supply, reaching pH ≥ 6.0 within 3 weeks after the second OC addition. Treatments with low OC additions showed slower pH increases, reaching values between pH 5.5 and 6.0 after one year. The control treatment had pH values <5.0 at the end of the experiment. After one year of anoxic incubation, the control treatment lost 10% of the native OC. Treatments with OC additions lost between 13 and 19% of total OC (native + added OC), with higher percentage loss in treatments with high OC additions.Highest losses were observed for the non mineral-associated OC fraction (up to 69% in treatments with high OC additions), with up to 20% being converted to the mineral-associated OC. OC composition changed little compared to the start of the experiment, showing slightly reduced proportions of carbohydrates (≤10% loss) and slightly higher proportions of lipids and lignin.Best remediation success was achieved by adding 50% of the native soil OC as wheat straw, resulting in fast pH neutralization, strongly reducing conditions, and decreased sulfur and iron concentrations in the soil solution. However, the amount of bioavailable OC was reduced to one third after the incubation period. Repeated OC addition is therefore recommended to keep the total amount of bioavailable, undecomposed plant residues high and to ensure long-term remediation success.

Stabilization dynamics of easily and poorly soluble Zn compounds in the soil

Stabilization mechanisms of easily and poorly soluble Zn compounds in Haplic Chernozem are considered in a long-term incubation experiment, including the dissolution and hydrolysis of the Zn added compounds (acetate, nitrate, sulphate, chloride, phosphate, and oxide) at a rate of 300 and 2000 mg kg –1 and the following post-sorption metal transformation. The indicators of stabilization were changes in the content of Zn weakly bound compounds (WBCs) and soil pH. Stabilization of Zn acetate, nitrate, sulphate, chloride progressed during incubation for 5 years which resulted in a decrease of Zn WBCs and an increase in soil pH. In the soil contaminated with Zn phosphate and oxide, the content of Zn WBCs increased and the soil pH decreased with time.

Bioavailable dissolved organic matter and its spatio-temporal variation in a river dominated tropical brackish water Lagoon, India

Bioavailable dissolved organic carbon (BDOC), nitrogen (BDON) and their degradation rate constants were measured for the Chilika Lagoon, India. Long-term laboratory incubation experiments (90 days) were conducted at a constant temperature (25 °C) to quantify the bioavailable dissolved organic matter (DOM) and the possible degradation rate coefficients. The results showed that 41 ± 12% of dissolved organic carbon (DOC) and 47 ± 17% of dissolved organic nitrogen (DON) were BDOC and BDON respectively, with their stoichiometry found to be higher than the Redfield ratio. A first order exponential non-linear fitting routine was used to estimate pool sizes. The degradation rate constant (k) for the BDOC varied from 0.127–0.329 d−1 and BDON from 0.043–0.306 d−1 during the study period. Half-lives of the BDOC and BDON ranged from 2.1–5.4 and 2.2–15.9 days, respectively. Overall, the results showed that a fraction of the labile DON was transported from the lagoon to the adjacent coastal sea.

Temperature sensitivity of soil organic carbon decomposition increased with mean carbon residence time: Field incubation and data assimilation.

Temperature sensitivity of soil organic carbon (SOC) decomposition is one of the major uncertainties in predicting climate-carbon (C) cycle feedback. Results from previous studies are highly contradictory with old soil C decomposition being more, similarly, or less sensitive to temperature than decomposition of young fractions. The contradictory results are partly from difficulties in distinguishing old from young SOC and their changes over time in the experiments with or without isotopic techniques. In this study, we have conducted a long-term field incubation experiment with deep soil collars (0-70cm in depth, 10cm in diameter of PVC tubes) for excluding root C input to examine apparent temperature sensitivity of SOC decomposition under ambient and warming treatments from 2002 to 2008. The data from the experiment were infused into a multi-pool soil C model to estimate intrinsic temperature sensitivity of SOC decomposition and C residence times of three SOC fractions (i.e., active, slow, and passive) using a data assimilation (DA) technique. As active SOC with the short C residence time was progressively depleted in the deep soil collars under both ambient and warming treatments, the residences times of the whole SOC became longer over time. Concomitantly, the estimated apparent and intrinsic temperature sensitivity of SOC decomposition also became gradually higher over time as more than 50% of active SOC was depleted. Thus, the temperature sensitivity of soil C decomposition in deep soil collars was positively correlated with the mean C residence times. However, the regression slope of the temperature sensitivity against the residence time was lower under the warming treatment than under ambient temperature, indicating that other processes also regulated temperature sensitivity of SOC decomposition. These results indicate that old SOC decomposition is more sensitive to temperature than young components, making the old C more vulnerable to future warmer climate.

Coupled effect of temperature and mineral additions facilitates decay of aspen bark

Tree bark represents a substantial component of coarse woody debris (CWD) in boreal forests. Estimating its decay rates improves our understanding of decomposition processes of woody debris and their effects on the forest carbon cycle. The atmospheric deposition of nitrogen (N) and phosphorus (P) from aerosols and gases has notably grown during the last century. We examined the effect of mineral N and P additions and temperature on the decay rate of aspen (Populus tremula) bark in a long-term incubation experiment at constant and sufficient moisture level.Fresh aspen bark with natural moisture was mixed with local soil (Haplic Phaeozems) in proportion of 2:1 by dry mass to prepare the soil-bark substrates (SBSs). Mineral elements (N and P) were added to the SBSs with a proportion of 1% of dry bark weight (for each element). The following treatments of SBS's were studied: (1) Bark+Soil, pure SBS (control); (2) Bark+Soil+N; (3) Bark+Soil+N+P and (4) pure soil, S. The SBSs were incubated in thermostats at 2, 12 and 22°С for 12months. The decay rate of SBSs (DecR, mgСkg−1h−1) was measured by an infrared gas analyzer at least 1–2 times per week. Total carbon losses (TotL-C, gСkg−1 of bark) were estimated using the accumulative curves of DecR throughout the experiment for each treatment. The decay constants (k) were calculated based on the single exponential model. The temperature sensitivity of the DecR was estimated using the temperature coefficient Q10.Mineral N and P additions decreased the C:N and increased the Lignin : Cellulose ratios during the long-term incubation of aspen bark and caused a considerable increase in the DecR, k values, TotL-C values, and consequently a decrease of the turnover time. The maximal values of TotL-C were attributed to the SBS-NP treatment at 22°С and comprised 72% of the initial C content in bark. The turnover time of soil-bark substrates varied from 2 to 7.3years depending on the treatment and temperature. The increase of the incubation temperature from 2 to 12°C and from 12 to 22°C caused a similar effect on the DecR over 12months of the experiment, and the Q10 in different treatments varied negligibly: from 1.21 to 1.37. The temperature effect was most significant only during the first 1–2months of experiment, explaining ca. 83% of the mean DecR variance whereas the ‘Treatment’ factor was attributed for 76–83% of the mean DecR variance in later stages (3–12months) of decay of aspen bark. A close relationship between the Lig:Cel ratio and DecR was observed during 1–2months of incubation. We conclude that the effect of mineral additions on the decay rate of aspen bark is more important than the effect of temperature. The coupled effect of N and P additions was more pronounced than the effect of N addition alone.

Long-term effects of sulfidized silver nanoparticles in sewage sludge on soil microflora.

The use of silver nanoparticles (AgNPs) in consumer products such as textiles leads to their discharge into wastewater and consequently to a transfer of the AgNPs to soil ecosystems via biosolids used as fertilizer. In urban wastewater systems (e.g., sewer, wastewater treatment plant [WWTP], anaerobic digesters) AgNPs are efficiently converted into sparingly soluble silver sulfides (Ag2 S), mitigating the toxicity of the AgNPs. However, long-term studies on the bioavailability and effects of sulfidized AgNPs on soil microorganisms are lacking. Thus we investigated the bioavailability and long-term effects of AgNPs (spiked in a laboratory WWTP) on soil microorganisms. Before mixing the biosolids into soil, the sludges were either anaerobically digested or directly dewatered. The effects on the ammonium oxidation process were investigated over 140 d. Transmission electron microscopy (TEM) suggested an almost complete sulfidation of the AgNPs analyzed in all biosolid samples and in soil, with Ag2 S predominantly detected in long-term incubation experiments. However, despite the sulfidation of the AgNPs, soil ammonium oxidation was significantly inhibited, and the degree of inhibition was independent of the sludge treatment. The results revealed that AgNPs sulfidized under environmentally relevant conditions were still bioavailable to soil microorganisms. Consequently, Ag2 S may exhibit toxic effects over the long term rather than the short term. Environ Toxicol Chem 2017;36:3305-3313. © 2017 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.

Interactions of riverine suspended particulate matter with phosphorus inactivation agents across sediment-water interface and the implications for eutrophic lake restoration

Phosphorus (P) inactivation agents (PIAs) have been widely used in lakes for eutrophic management. However, the interactions of riverine suspended particulate matter (SPM) with PIAs have not been elucidated to the point of complete confidence in the success of PIA application to eutrophic lakes. In this study, a long-term field incubation experiment was carried out to investigate the effects of riverine SPM on sediment internal P management. Fluorescence excitation emission matrix coupled with parallel factor (EEM–PARAFAC) was used to characterize dissolved organic matter (DOM) derived from SPM/sediment, and to study its complexation with La (III) and Ca (II) contained in two PIAs. The analysis identified one protein-and two humic-like components in these samples, which show variable quenching effects by La (III) and Ca (II). The continuous settling of SPM can bury PIAs deeper into the sediment layers and while increasing the mobile P content in surface sediments. This consequently made an increase of P fluxes and surface sediment reactivity, which was witnessed by the increased labile P concentration measured by diffusive gradient in film (DGT). However, the binding capacity of PIAs towards sediment mobile P was kept in a buried layer during the six months’ field experiment. This study indicates that the influence mechanism of riverine SPM on PIAs was through a decrease of the reactive sorption sites of PIAs by complexing with DOM and continuously increasing the mobile P content in surface sediment thereby largely surpassing their maximum P sorption capacity. Repeated dosing at scheduled times would be better for turbid eutrophic lake remediation with high input of riverine SPM in long-term management.

Effect of temperature and moisture on the mineralization and humification of leaf litter in a model incubation experiment

The mineralization and humification of leaf litter collected in a mixed forest of the Prioksko-Terrasny Reserve depending on temperature (2, 12, and 22°C) and moisture (15, 30, 70, 100, and 150% of water holding capacity ( WHC)) has been studied in long-term incubation experiments. Mineralization is the most sensitive to temperature changes at the early stage of decomposition; the Q 10 value at the beginning of the experiment (1.5–2.7) is higher than at the later decomposition stages (0.3–1.3). Carbon losses usually exceed nitrogen losses during decomposition. Intensive nitrogen losses are observed only at the high temperature and moisture of litter (22°C and 100% WHC). Humification determined from the accumulation of humic substances in the end of incubation decreases from 34 to 9% with increasing moisture and temperature. The degree of humification CHA/CFA is maximum (1.14) at 12°C and 15% WHC; therefore, these temperature and moisture conditions are considered optimal for humification. Humification calculated from the limit value of litter mineralization is almost independent of temperature, but it significantly decreases from 70 to 3% with increasing moisture. A possible reason for the difference between the humification values measured by two methods is the conservation of a significant part of hemicelluloses, cellulose, and lignin during the transformation of litter and the formation of a complex of humic substances with plant residues, where HSs fulfill a protectoral role and decrease the decomposition rate of plant biopolymers.

Changes in biochar physical and chemical properties: Accelerated biochar aging in an acidic soil

Biochar (BC) is increasingly used as soil amendment; however, its stability and alteration in the soil environment are still unclear. Here, we investigated BC decomposition and changes of BC characteristics during a long-term incubation experiment. 13C-depleted BCs were incubated for two years in an acidic Planosol and a calcareous Chernozem, respectively. BC decomposition inferred from the C isotope signature of the incubated materials was marginal. Yet, small angle X-ray scattering showed that the surface roughness of the BCs increased over time. Mid-infrared spectra indicated changes in the BCs' molecular characteristics upon aging. There was an overall increase of infrared bands assigned to H- and O-containing functional groups, especially carboxylic groups. Contact angle measurements revealed that the hydrophobic surfaces of freshly produced BCs became more hydrophilic during soil incubation. Our results suggest that BC aging is strongly influenced by soil traits. In the more acidic Planosol, these aging processes were accelerated.