Comparative evaluation of compost humic acids and their effects on the germination of switchgrass (Panicum vigatum L.)

Purpose

This study aimed to investigate comparatively the main chemical and physico-chemical properties of the humic acid (HA) fraction of three different composts and to evaluate the bioactive effects of these HAs on the germination and early growth of four populations of switchgrass.

Materials and methods

Three compost HAs isolated from a green compost (HA_GC), a mixed compost (HA_MC), and a coffee compost (HA_CC) were characterized for some chemical and physico-chemical properties, such as ash content, elemental composition, total acidity, carboxylic and phenolic OH group contents, E₄/E₆ ratio, Fourier Transform infrared (FT IR), and fluorescence spectroscopies. In subsequent experiments conducted in vitro in a climatic chamber under controlled conditions, the bioactive effects of the three HAs at concentrations of 10, 50, and 200 mg?L^?1 were tested on the germination and early growth of four switchgrass (Panicum virgatum L.) populations, the octaploids Shelter, Shawnee and Dacotah, and the tetraploid Alamo.

Results and discussion

The ash content and the E₄/E₆ ratio were, respectively, much higher or slightly higher for HA_CC than for the other two HAs. HA_MC showed the lowest C and H contents and the highest O content, whereas HA_GC had the highest N content. The total acidity and phenolic OH group content followed the order: HA_MC?>?HA_CC?>?HA_GC. The fluorescence analysis of the three HAs evidenced a common fluorophore unit possibly associated to simple aromatic structures, such as phenolic-like, hydroxy-substituted benzoic and cinnamic acid derivatives. The FT IR spectra of all HA samples indicated the presence of aromatic phenolic structures. Significant beneficial effects were produced by any HA on switchgrass germination and early growth as a function of the population tested and the HA dose.

Conclusions

Results of this study demonstrated that the addition of compost HAs to the germination medium of four switchgrass populations positively influenced the germination process and the growth of primary root and shoot. Significant correlations were found between HA bioactivity and some HA properties. These results suggest a possible use of compost as soil amendment in areas where switchgrass grows naturally or is cultivated.     

Does the compositional change of soil organic matter in the rhizosphere and bulk soil of tea plants induced by tea polyphenols correlate with Pb bioavailability?

Purpose

Soil organic matter (SOM) plays a vital role in controlling metal bioavailability. However, the relationship between SOM and its fractions, including water-soluble substances (WSS), fulvic acid (FA), humic acid (HA), and soil microbial biomass (SMB), to metal bioavailability in plants has not been thoroughly investigated. This study examined the compositional change of SOM after tea polyphenols (TPs) were added to the soil and its correlation with Pb bioavailability.

Materials and methods

Ultisol samples were collected from Fuyang, spiked with two levels (0 and 300 mg kg^?1 DW) of Pb, and aged for 30 days. Four uniform seedlings were transplanted to each plastic pot, which were filled with 3 kg of air-dried soil. After successful transplantation, three levels (0, 300, and 600 mg kg^?1 DW) of TPs were amended as irrigation solution for the pots. The Pb concentrations in different tissues of the tea plants were determined after 6 months. SOM, WSS, FA, HA, and SMB were extracted and quantified using a Multi N/C Total Organic Carbon Analyser.

Results and discussion

Adding TPs to Pb-polluted soils alleviated Pb toxicity to microorganisms and increased SMB and the rhizosphere effect. The rhizosphere SOM was lower than bulk SOM in Pb-unspiked soils, while the opposite results were observed in Pb-spiked soils. A similar inconsistency for HA in the rhizosphere and bulk soil between Pb-unspiked and Pb-spiked soils might explain the difference in SOM. FA increased with the addition of TPs in both the rhizosphere and bulk soils, which might be the result of TP transformation. Positive correlations are present between the compositions of rhizosphere SOM and Pb in different tissues of the tea plant. SMB correlated negatively with Pb in young leaves and stems. Compared to rhizosphere soil, SOM components in bulk soil were less strongly correlated with Pb in tea plants.

Conclusions

Addition of TPs to soil changes the components of SOM and Pb bioavailability. SOM and its fractions, including WSS, FA, HA, and SMB, show a close relationship to Pb in different tissues of the tea plants.     

Short-term effect of cultivation and crop rotation systems on soil quality indicators in a coastal newly reclaimed farming area

Purpose

Soil quality (SQ), a measure of the sustainability of land use and soil management practices, can be assessed by indicators including soil physical, chemical, and biological properties. Our primary objectives were to investigate the influence of consecutive cultivation and different crop rotation systems on individual SQ indicators and to examine the impact of rotation systems on SQ using soil quality index (SQI) model.

Materials and methods

A site-specific selection of 17 potential SQ indicators representing soil chemical and physical attributes (0–10 cm) and groundwater features on 60 sampling locations and 10 representative soil profiles was chosen in a typical coastal newly reclaimed farmland of north Jiangsu Province, China. Using ANOVA analysis, the crop rotation effect was analyzed by comparing SQ indicators between rice/rape rotation soil and cotton/barley rotation soil. An overall SQI was calculated to examine whether plant biomass indices exactly responded to the SQI value.

Results and discussion

Results indicated that cultivation had significant effect on some soil profile characteristics, including SOM, SOCD, AP, CEC, AK, EC_e, and I _f. Crop rotation systems also had significant influence on some SQ indicators. Compared with cotton/barley rotation soil, rice/rape rotation soil was characterized by higher organic matter, undifferentiated nutrient storage and salinity/alkalinity, lower water accommodation and infiltration, and adverse groundwater conditions. Cotton/barley rotation had higher SQI values over rice/rape rotation (0.523 vs. 0.422). SQ indicators of SAR_e, EC_e, and WT_g contributed the most to the overall SQI value for each rotation system. Plant biomass indices significantly correlated with the SQI values for both rotation systems, suggesting that the SQI values essentially reflected the status of SQ.

Conclusions

Such results allowed us to conclude that cotton/barley rotation system contributed more to the improvement of SQ than rice/rape rotation system in coastal farming area. Also, we suggested SOCD, AK, ρ _b, WT_g, and EC_g as the minimum data set for SQ assessment, as they had potential in discriminating the effect of rotation systems on SQ between the rotation systems used here.     

Effect of biosolid application to Mollisol Chilean soils on the bioavailability of heavy metals (Cu,Cr, Ni,and Zn) as assessed by bioassays with sunflower (Helianthus annuus) and DGT measurements

Purpose

This study assessed the effect of biosolid application on the bioavailable fraction of some trace elements (Cu, Cr, Ni, and Zn) using a bioassay with sunflower (Helianthus annuus) and a chemical assay, diffusion gradient in thin films (DGT).

Materials and methods

Five surface soil samples (0–20 cm) were collected from an agricultural zone in Central Chile where biosolids are likely to be applied. Municipal biosolids were mixed with the soil at concentrations of 0, 30, 90, and 200 Mg ha^?1. The experiment to determine the bioavailability of metals in the soil using the bioassay was performed using sunflower. The DGT technique and Community Bureau of Reference (BCR) sequential extraction were used to determine the bioavailable fractions of the metals.

Results and discussion

The application of biosolids increased the phytoavailability of Zn, Ni, and Cr in most of the soils, as indicated by the increasing concentrations in sunflower plants as the biosolid application rate increased. In two of the soils, Codigua and Pelvín, this increase peaked at an application rate of 90 Mg ha^?1. Decreases in the bioavailable fractions of Zn, Ni, and Cr were observed with higher biosolid application rates. The bioavailability of metals was estimated through multiple linear regression models between the metals in the sunflower plants and the different chemical fractions of metals in the soils treated with different biosolid rates, which displayed a positive contribution of the labile (water soluble, carbonate, and exchangeable), oxide, and organic metal forms in the soil, particularly with respect to Ni and Zn at application rates of 30 and 90 Mg ha^?1. The bioavailable fraction of metals was determined in soils using the DGT technique. The effective concentration (C _E) results were compared with those in sunflower plants. The DGT technique could effectively predict the bioavailable fractions of Cr, Ni, and Zn in the Taqueral soil but only that of Zn in the Polpaico soil.

Conclusions

The application of biosolids significantly increased the labile fraction of most of the metals in the studied soils, particularly at the highest biosolid application rate. C _E increased as the concentration of biosolids increased for most of the metals. The effectiveness of the DGT technique for predicting the bioavailability of metals was dependent on the soil type and the metal. However, the C _E for soil Cu was not related to plant Cu for all soils studied.     

HS-protein associates in the aqueous/oil system: composition and colloidal properties

Purpose

Despite experiments with humic substances and positively charged proteins, the colloidal behavior of HS-protein mixture in the system of two immiscible liquids has been neglected. In this context, the main objective of this study was to reveal the interference of HS and globular proteins on its partition in an aqueous/organic liquid system and the adsorption at liquid/liquid interface as a model of natural organic matter interaction with proteins in nature at hydrophobic/hydrophilic surfaces.

Materials and methods

Coal humic acids (HA) and two globular proteins lysozyme and albumin were under the test. Aqueous phase was prepared in phosphate-buffered saline (pH 7.2?±?0.1, 0.16 M); p-xylene was chosen as an organic phase. Experiments were performed for fixed concentration of protein (0.1 g L^?1 for lysozyme and 0.06 g L^?1 for albumin) and varied HA concentration from 0.2 to 50 mg L^?1. Radiotracer method including tritium thermal activation and scintillation phase method, dynamic light scattering, and optical microscopy were used to control mixed adsorption layer at the aqueous/p-xylene interface and composition of each contact phase.

Results and discussion

The results suggest that if both HA and protein are negatively charged (HA-albumin mixture), the mechanism of interaction between them in the bulk of water and at liquid/liquid interface is controlled by HA concentration. At low HA concentrations, free protein prevents HA adsorption at liquid/liquid interface and its transition to the organic phase via coulomb repulsion. At high HA concentration, the formation of hydrophilic complexes occurs via both electrostatic attraction between positively charged amino acid residues and the hydrophobic interaction. In HA-lysozyme mixture, the interaction between protein and HA is preferably provided by electrostatic attraction that provides higher hydrophobicity of HA-lysozyme complex compared with free HA. An increase in HA concentration results in partial recharge of the conjugate that leads to lysozyme amount reduction at the interface. We also measured the composition of spontaneously formed precipitate of HA-lysozyme conjugate and followed its self-organization.

Conclusions

This work demonstrates colloidal chemical behavior of net positively and negatively charged model protein by coal humic acids under environmentally relevant solution conditions in the system of two immiscible liquids that were used as a model of natural membrane. For the first time, quantities of both protein and HA in mixed adsorption layer at the liquid/liquid interface in the cases of positively and negatively charged protein have been determined.     

The role of stromatolites in explaining patterns of carbon, nitrogen, phosphorus, and silicon in the Se?ovlje saltern evaporation ponds (northern Adriatic Sea)

Purpose

In summer 2007, biweekly benthic fluxes of the biogenic elements carbon (C), nitrogen (N), silicon (Si), and phosphorus (P) were studied in the Se?ovlje saltern (salt-making facility) in the northern Adriatic Sea, Slovenia in order to determine the impact of stromatolite (??petola??) on the geochemical properties of saltern sediments.

Materials and methods

The brine and pore waters were analyzed for salinity, NH ₄ ⁺ , NO ₃ ^? , PO ₄ ^3? , SiO ₄ ^4? , total dissolved nitrogen, total dissolved phosphorus, and fluorescent dissolved organic matter. The sediment was analyzed for organic carbon (OC), total nitrogen (TN), total and organic phosphorus (OP), and biogenic Si concentrations, as well as values of ?? ¹³C_OC and ?? ¹⁵N_TN.

Results and discussion

Nutrient concentrations in brine water increased along the salinity gradient due to different processes, such as the evaporative concentrations of seawater, bacterial activity, more pronounced transformation and degradation of organic matter, and regeneration of nutrients. The petola from the Se?ovlje saltern, which is predominately composed of cyanobacterial and diatom communities, develops during the early evaporation stage and survives during high salinity and halite crystallization. Nitrogen fixation and P removal were the principal biogeochemical processes controlling dissolved inorganic N and P concentrations. At higher salinities, N limitation was more important. Microbes decomposed at higher salinities, and the remineralized N and P nutrients were released from surface pore waters to the brine. OP remineralization was also an important process influencing the distribution of PO ₄ ^3? concentrations in pore waters deeper in the sediments. The increasing SiO ₄ ^4? concentrations with increasing salinity in the brine waters were due to dissolution of diatom frustules, while the decrease in pore water SiO ₄ ^4? was probably the consequence of microbial uptake.

Conclusions

This study provides a better understanding of nutrient cycling and the geochemical processes in the Se?ovlje saltern.     

Applying a GLM-based approach to model the influence of soil properties on the toxicity of phenmedipham to Folsomia candida

Purpose

Soil properties are the main explanation to the different toxicities obtained in different soils due to their influence on chemical bioavailability and the test species performance itself. However, most prediction studies are centred on a few soil properties influencing bioavailability, while their direct effects on test species performance are usually neglected. In our study, we develop prediction models for the toxicity values obtained in a set of soils taking into account both the chemical concentration and their soil properties.

Materials and methods

The effects on the avoidance behaviour and on reproduction of the herbicide phenmedipham to the collembolan Folsomia candida is assessed in 12 natural soils and the Organisation for Economic Co-operation and Development (OECD) artificial soil. The toxicity outcomes in different soils are compared and explanatory models are constructed by generalised linear models (GLMs) using phenmedipham concentrations and soil properties.

Results and discussion

At identical phenmedipham concentrations, the effects on reproduction and the avoidance response observed in OECD soil were similar to those observed in natural soils, while effects on survival were clearly lower in this soil. The organic matter and silt content explained differences in the avoidance behaviour in different soils; for reproduction, there was a more complex pattern involving several soil properties.

Conclusions

Our results highlight the need for approaches taking into account all the soil properties as a whole, as a necessary step to improve the prediction of the toxicity of particular chemicals to any particular soil.     

Characteristic Variation of Concentration and Chemical Form in Sulfur, Nitrate, Ammonium, and Chloride Species Observed at Urban and Rural Sites of Japan

A field survey on the concentration of chemical species in particulate matter and gaseous compounds at two monitoring sites with different site classifications (urban and rural) was conducted over three years. Total (particulate matter + gaseous compounds) concentrations at the rural site were significantly lower than those at the urban site for all species (sulfur $\left( {{\text{SO}}^{{{\text{2 - }}}}_{{\text{4}}} {\left( {\text{p}} \right)}} \right.$ and SO₂(g)), nitrate ${\text{(NO}}_{{{\text{3}}^{{\text{ - }}} }} {\left( {\text{p}} \right)}$ and HNO₃(g)), ammonium ${\text{(NH}}_{{{\text{4}}^{{\text{ + }}} }} {\text{(p)}})$ and ammonia (NH₃(g)), and chloride (Cl^? (p) and HCl (g))), which is thought to reflect classification of the site. The difference in the sulfur concentration at the urban and rural sites was characterized by the difference in SO₂ (g) concentration. Further, a clear seasonality was observed for the nitrate species. The HNO₃ (g) concentration was high in the summer compared with other seasons at both the urban and rural sites. The ${\text{NH}}_4^ + \left( {\text{p}} \right)$ concentration levels were approximately the same as those of NH₃ (g) at both sites. The molar ratios of the particulate matter concentration to the total concentration showed different characteristics; the nitrate, ammonium and ammonia, and chloride species showed a clear seasonal variation: low in summer and high in winter and the values were similar regardless of the site. On the other hand, the sulfur species showed constant values at both the urban and rural sites, however the concentrations were significantly different for the two sites. Ammonium accounted for the largest proportion of cations in the particulate matter, regardless of the site classification. In contrast, ${\text{SO}}_4^{2 - } \left( {\text{p}} \right)$ accounted for the largest proportion of anions at the rural site, whereas ${\text{NO}}_3^ - \left( {\text{p}} \right)$ was comparable to ${\text{SO}}_4^{2 - } \left( {\text{p}} \right)$ at the urban site. Ammonia accounted for the largest proportion of all chemical species at both sites. Seasonal analysis of the proportional distribution in particulate matter and gaseous compounds provides information on atmospheric conditions.     

Acute toxicity of zinc and arsenic to the warmwater aquatic oligochaete <Emphasis Type="Italic">Branchiura sowerbyi</Emphasis> as compared to its coldwater counterpart <Emphasis Type="Italic">Tubifex tubifex</Emphasis> (Annelida,Clitellata)

Purpose

This study aimed at evaluating the acute effects of arsenic and zinc to the warmwater aquatic oligochaete Branchiura sowerbyi. Relative sensitivity with the coldwater species Tubifex tubifex was compared. Implications for the use of B. sowerbyi in the risk assessment of sediments in the tropics are discussed.

Materials and methods

Water-only (96 h) and sediment (14 days) toxicity tests were conducted with both species evaluating a concentration series of arsenic and zinc. The tests were conducted considering the environmental conditions in the natural habitat of T. tubifex (predominantly temperate) and B. sowerbyi (predominantly tropical). Both lethal and sublethal endpoints (autotomy of the posterior body parts, abnormal behavior and appearance) were determined in the tests. The lethal (LC₁₀ and LC₅₀) and effect (EC₁₀ and EC₅₀) concentrations were also determined to assess metal sensitivity for both species.

Results and discussion

Both test species were more sensitive to Zn than As in water-only tests, which is in agreement with previous studies evaluating the toxicity of these metals to aquatic oligochaetes. Sublethal effects were generally noted at concentrations lower than those leading to mortality. The warmwater oligochaete B. sowerbyi was more sensitive to both metals tested than the coldwater species T. tubifex.

Conclusions

Study findings support the need for using indigenous tropical species in risk assessments in the tropics. In addition, sublethal effect parameters should be included in toxicity testing with aquatic oligochaetes.

     

Investigating particle concentration effects of polycyclic aromatic hydrocarbon (PAH) sorption on sediment considering the freely dissolved concentrations of PAHs

Purpose

Suspended particulate sediment (SPS) concentration has a great impact on the sediment to water partitioning coefficients (K _p) of hydrophobic organic compounds (HOCs), which is called the particle concentration effect (PCE). However, the mechanisms regarding the PCE are not yet well understood, and there is little direct experimental evidence for these mechanisms. The aim of this study was to investigate the PCE of polycyclic aromatic hydrocarbon (PAH) sorption on sediment by analyzing the freely dissolved concentrations of PAHs.

Materials and methods

Sediments were collected from the Yellow River and the Haihe River in China. Pyrene was selected as a model PAH to investigate the sorption of PAH on sediments. In addition to the total dissolved concentration (C _TW) of pyrene, the freely dissolved concentration (C _FW) measured by polyethylene devices was used to investigate the PCE of pyrene in the presence and absence of phenanthrene and chrysene.

Results and discussion

For both the Haihe River and Yellow River sediments, in the presence and absence of other PAHs, the K _p value of pyrene with C _FW as the equilibrium concentration in the water phase was approximately two times higher than that with C _TW as the equilibrium concentration. With either C _TW or C _FW as the equilibrium concentration in the water phase, the K _p value of pyrene decreased with increasing SPS concentration as a power function. In addition, the K _p value with C _TW as the equilibrium concentration decreased faster than that with C _FW. This inferred that, apart from a third phase including dissolved organic carbon (DOC) and colloids, particle–particle, or particle–DOC interactions were important for the PCE. The contribution of the third phase to the PCE for the Haihe River sediment (72.5?±?26.4 %) was greater than the contribution for the Yellow River sediment (48.4?±?16.2 %), which had a larger particle size and lower total organic carbon and black carbon contents.

Conclusions

The PCE of PAH sorption onto sediments was attributed to both the third phase and to particle–particle or particle–DOC interactions. The contribution of the third phase to the PCE depended on both the TOC content and the particle size of sediment. As high SPS and DOC concentrations exist in many rivers, their effects on the sorption of HOCs should be considered when conducting bioavailability and ecological risk assessment.     

Ecophysiological status of different growth stage of understorey Acacia leiocalyx and Acacia disparrima in an Australian dry sclerophyll forest subjected to prescribed burning

Purpose

Understorey Acacia spp. plays an important role in post-fire restoration because these understorey plants are tolerant to stress conditions. We investigated how the ecophysiological status of two species of understorey, Acacia leiocalyx and Acacia disparrima, varied depending on the plant growth stage after prescribed burning.

Materials and methods

Plants were grouped in different size classes, namely seedlings, small and medium sizes, and physiological variables such as foliar gas exchange, water use efficiency and light dependency were measured at two experimental sites subjected to prescribed burning.

Results and discussion

A. leiocalyx showed higher symbiotic N₂ fixation and photosynthetic capacity compared to A. disparrima regardless of plant-size classes at both experimental sites. This could explain the greater relative growth rate of A. leiocalyx than that of A. disparrima. However, A. disparrima is more tolerant to shady conditions than A. leiocalyx.

Conclusions

This finding may be an indication of how well these two species recover after fire, although A. leiocalyx may have faster regrowth, as it is fixing more N.     

Kinetics of the reaction between the hydroxyl radical and organic matter standards from the International Humic Substance Society

Purpose

The objective of this study was to evaluate the effect of the physicochemical properties of five dissolved organic matter (DOM) isolates on their reactivity with the hydroxyl radical (HO·) in water.

Materials and methods

Five DOM isolates were purchased from the International Humic Substance Society (IHSS). Weight average molecular weight (M _W) of these samples was quantified using size exclusion chromatography based on polyethylene glycols as reference standards. Functional group and elemental composition of the DOM samples were available from the IHSS website. Room temperature rate constants were measured using electron pulse radiolysis.

Results and discussion

Five IHSS standards were examined in this study: two soil organic and three aquatic organic matters. The composition varied from samples that had primarily aliphatic carbon (Pony Lake fulvic acid) to mostly aromatic carbon moieties (Elliot Soil humic acid). The M _W values of the five samples ranged from 2,400 to 4,100 Da, with an average value of 3,060 Da. Second-order reaction rate constants between DOM and HO· (k _DOM-HO·) were measured using thiocyanate competition kinetics, giving values ranging from 1.21 to 10.36?×?10⁸ M_C ^?1?s^?1. The k _DOM-HO· values were not found to correlate with either M _W or the aliphatic-aromatic carbon ratio, which is consistent with previous reports looking at natural organic matter (NOM), but is different to reports on size-fractionated (ultrafiltration through 15–1 kDa membranes) effluent organic matter (EfOM). We attribute this difference to the larger molecular weight distributions in size-fractionated EfOM compared to NOM.

Conclusions

The k _DOM-HO· values in this study ranged over a factor of 10, suggesting that hydroxyl radical reactivity does depend on the sample composition; however, no major correlation was found between the measured reactivity and bulk physicochemical properties of DOM.     

Environmental impact of two organic amendments on sorption and mobility of propachlor in soils

Purpose

The purposes of this study were to understand the sorption?Cdesorption characteristics of propachlor in three types of soils with added solid organic matters and the effect of solid organic matters on propachlor mobilization in soil microstructures.

Materials and methods

Three soil types, Eutric gleysols (EG), Hap udic cambisols (HUC), and Haplic alisol (HA), along with the lakebed sludge (SL) and pig manure compost (PMC), were used in the study. The sorption and desorption experiments were carried out using the standard batch equilibration method. Soil column leaching was performed with soil samples packed into PVC columns. Soil thin-layer chromatography was performed using soils and water mixture spread on a 0.5?C0.7-mm thick layer over 20?×?10-cm glass plates.

Results and discussion

Propachlor was shown to be more mobile in EG and HUC than in HA. Application of PMC and SL to soils affected the propachlor mobilization in the soils. Using batch experiment, soil column, and soil thin-layer chromatography, we showed that addition of SL and PMC increased the sorption and decreased desorption of propachlor in the soils. Addition of PMC and SL reduced the total concentration of propachlor in the soil leachate and migration of propachlor in the soil profiles. Physicochemical properties of the three soils were analyzed and showed that the content of organic carbon (in percentage) was higher in Haplic alisol than in Eutric gleysols and Hap udic cambisols.

Conclusion

The soil organic matter played critical roles in modifying the absorption and mobility of organic chemicals (e.g., herbicide and contaminants) in soil ecosystem.     

Influence of mixtures of acenaphthylene and benzo[a]anthracene on their degradation by Pleurotus ostreatus in sandy soil

Purpose

Polycyclic aromatic hydrocarbons (PAHs) are a class of organic compounds commonly found as soil contaminants. Fungal degradation is considered as an environmentally friendly and cost-effective approach to remove PAHs from soil. Acenaphthylene (Ace) and Benzo[a]anthracene (BaA) are two PAHs that can coexist in soils; however, the influence of the presence of each other on their biodegradation has not been studied. The biodegradation of Ace and BaA, alone and in mixtures, by the white rot fungus Pleurotus ostreatus was studied in a sandy soil.

Materials and methods

Experimental microcosms containing soil spiked with different concentrations of Ace and BaA were inoculated with P. ostreatus. Initial (t ₀) and final (after 15 days of incubation) soil concentrations of Ace and BaA were determined after extraction of the PAHs.

Results and discussion

P. ostreatus was able to degrade 57.7% of the Ace in soil spiked at 30 mg kg^?1 dry soil and 65.8% of Ace in soil spiked at 60 mg kg^?1 dry soil. The degradation efficiency of BaA by P. ostreatus was 86.7 and 77.4% in soil spiked with Ace at 30 and 60 mg kg^?1 dry soil, respectively. After 15 days of incubation, there were no significant differences in Ace concentration between soil spiked with Ace and soil spiked with Ace + BaA, irrespective of the initial soil concentration of both PAHs. There were also no differences in BaA concentration between soil spiked with BaA and soil spiked with BaA + Ace.

Conclusions

The results indicate that the fungal degradation of Ace and BaA was not influenced by the presence of each other’s PAH in sandy soil. Bioremediation of soils contaminated with Ace and BaA using P. ostreatus is a promising approach to eliminate these PAHs from the environment.     

Formation and distribution of methylmercury in sediments at a mariculture site: a mesocosm study

Purpose

The aim of the present study was to investigate the differences of methylmercury (MeHg) formation and distribution between mariculture (aquaculture) sediments (MS) and reference sediments (RS) collected from a site in Hong Kong.

Materials and methods

The MS and RS samples were split into four batches, three of which were spiked with HgCl₂ aqueous solution to a concentration of 0.8, ,2 and 8 mg k g^?1 in sediment samples SP1, SP2, and SP3, respectively, while the rest served as a control batch (referred to as C).

Results and discussion

The results showed that the highly Hg-polluted sediment produced greater amounts of MeHg. During the culture period, MeHg concentrations in sediments decreased over time. The decreasing percentage increased in the order of SP3?<?SP2?<?SP1, which might be due to the inhibition of MeHg degradation by high Hg concentrations. The mean value of MeHg concentrations and %MeHg of the total Hg (THg) in MS was significantly lower than those in RS, possibly due to the complexation of Hg with organic ligands, leading to lower Hg bioavailability for methylation bacteria. The distribution coefficient of THg (K_dT) was relatively high in MS compared to RS, indicating that the former had a greater number of binding sites for Hg adsorption.

Conclusions

Methylmercury formation was inhibited in MS, probably due to increased complexation of Hg²⁺ with organic matter and adsorption of Hg to MS. Furthermore, the mean value of K_dT in MS was relatively high when compared to RS, which illustrates that MS sediments have more binding sites than RS for adsorption of Hg.     

Differences in sorption behavior of the herbicide 4-chloro-2-methylphenoxyacetic acid on artificial soils as a function of soil pre-aging

Purpose

The sorption behavior of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) to three different artificial soil mixtures was investigated. Artificial soils serve as model systems for improving understanding of sorption phenomena.

Materials and methods

The soils consisted of quartz, ferrihydrite, illite, montmorillonite, and charcoal. In a previous study, several selected mixtures had been inoculated with organic matter, and microbial aging (incubation) had been performed for different periods of time (3, 12, and 18?months) before conducting the sorption experiments. The effect of this pre-incubation time on the sorption behavior was determined. Interaction of MCPA with soil surfaces was monitored by aqueous phase sorption experiments, using high-performance liquid chromatography/ultraviolet and in selected cases Fourier-transformed infrared spectroscopy.

Results and discussion

The sorption behavior showed large differences between differently aged soils; Freundlich and linear sorption model fits (with sorption constants K _f , 1/n exponents, and K _d values, respectively) were given for pH?=?3 and the unbuffered pH of ??7. The largest extent of sorption from diluted solutions was found on the surfaces with a pre-incubation time of 3?months. Sorption increased at acidic pH values.

Conclusions

Regarding the influence of aging of artificial soils, the following conclusions were drawn: young artificial soils exhibit stronger sorption at lower concentrations, with a larger K _f value than aged soils. A correlation with organic carbon content was not confirmed. Thus, the sorption characteristics of the soils are more influenced by the aging of the organic carbon than by the organic carbon content itself.     

Assessing metal bioaccumulation from estuarine sediments: comparative experimental results for the polychaete Arenicola marina

Purpose

The purpose of this paper is to compare three approaches for providing information on the bioaccumulation potential of metals from contaminated sediments to the deposit-feeding polychaete Arenicola marina.

Materials and methods

We present metal (Ag, As, Cd, Cu, Pb and Zn) bioaccumulation results from field-collected sediments quantified through direct measurements of bioaccumulated concentrations in A. marina over a period of 30 days under controlled laboratory exposures and compare these results with bioaccumulated metal concentrations in field-collected organisms from the same sites of collection of the sediments used in the laboratory exposures. For the metals for which model parameters are available (Ag, As, Cd and Zn), we also compare these results with biodynamic model predictions. We considered three UK estuaries characterised by a well-reported history of trace metal contamination and bioavailability in addition to the (control) site of collection of the worms.

Results and discussion

The results from laboratory-exposed organisms showed that the standard 28-day exposure duration may be adequate to identify the potential for metal bioaccumulation in this polychaete at the sites considered here. However, the time course of bioaccumulated concentrations and the comparison with measured concentrations in field-collected worms show that a steady state has not been reached, confirming the need for extended exposure periods. The worms showed symptoms of stress in feeding and growth during the initial 10 days of exposure and subsequent partial recovery during the following 20 days, suggesting that stress was not always caused by sediment contamination but that it was likely associated with handling and acclimation. At this last stage of the exposure, a generalised biodynamic model was used to provide estimates of bioaccumulated metal concentrations and net accumulation rates in worms.

Conclusions

The results of this study highlight the number of factors that should be considered for the interpretation of bioaccumulated metal concentrations in A. marina under laboratory exposures for contaminated sediment assessment, factors that appear to be common to most deposit-feeding polychaetes. A general biodynamic model proved to be a cost-effective method for an initial estimation of the extent and pattern of metal bioaccumulation under specified exposure conditions.     

Using in situ solid phase microextraction (SPME) for depth profiling in sediments treated with activated carbon

Purpose

Sediment contamination in US waterways is an expensive and complicated issue, and as acceptance of nontraditional sediment remediation strategies broadens, novel and efficient methods to assess and monitor the bioavailability of hydrophobic organic contaminants (HOCs) in contaminated sediments will play an important role.

Materials and methods

In this project, solid phase microextraction (SPME) fibers inside perforated steel tubes were used as in situ passive samplers to measure polycyclic aromatic hydrocarbon (PAH) concentrations in sediment before and after treatment with activated carbon (AC). Two modes of waterjet amendment injection were used to apply the AC. In the first treatment, a single 2-min injection was shot into the center of a test vessel, and in the second treatment, multiple 7-s injections in a grid were placed in sediment.

Results and discussion

In the single injection, no treatment was observed 5 cm away from the injection, while at 2.5 cm, >90 % decrease of PAH pore water concentration was observed, indicating a similar bioavailability decrease. In the multiple injection experiment, >90 % PAH pore water level reductions were observed throughout the test vessel. Highly contaminated and less contaminated sediments were mixed with 0–5 % AC by weight to develop AC treatment curves. Over 99 % reduction in PAH pore water concentrations and bioavailability was observed in the less contaminated sediment at 3 % AC, while 99 % reduction was never reached even at 5 % AC addition in the highly contaminated sediment. Different treatment curves were observed for the different contaminated sediments. In situ equilibration times were 120, 215, and 250 h for phenanthrene, pyrene, and benzo(a)anthracene, respectively.

Conclusions

The results show that in situ SPME is a viable method to observe AC treatment and evaluate reductions in pore water concentrations and bioavailability.     

Composition and spectroscopic characteristics of dissolved organic matter extracted from the sediment of Erhai Lake in China

Purpose

The content and composition of dissolved organic matter (DOM) in sediment directly affect nutrient cycling and material exchange in lake ecosystems. This study investigated the content and composition of DOM and its fractions in sediments, as well as the relationship between the different parameters and nitrogen (N) forms in DOM. The main aim of this study was to evaluate the compositional characteristics of DOM, hydrophobic bases (HOB), hydrophobic acids (HOA), hydrophobic neutral fractions (HON), and hydrophilic matter (HIM) in sediments from Erhai Lake, China.

Materials and methods

Seven surface sediment samples with different environmental characteristics were collected. The DOM in the sediment was fractionated into HOB, HOA, HON, and HIM using XAD-8 resin based on compound hydrophobicity. The contents of DOM and its fractions were measured using a TOC analyzer. The structural characteristics of DOM and its fractions were investigated using fluorescence spectroscopy and UV–Vis absorbance. Correlation analyses were carried out to better understand the relationships between the parameters of the spectral characteristics and the contents of the different N forms in DOM and its fractions.

Results and discussion

The content, spatial distribution and structure of DOM and its fractions in Erhai Lake sediment were affected by water depth and aquatic plants. The DOM content in sediment ranged from 0.2 to 0.5 g kg^?1. HON accounted for 41.3 to 85.7 % of DOM, whereas HIM constituted 15.0 to 58.7 % and was significantly negatively correlated with HON (R ² ?=?0.856, P?Conclusions (1) Hydrophobic fractions are the major components of DOM in the sediments from the seven sites in Erhai Lake. (2) DOM and its fractions mainly originated from microbial sources. (3) The A ₂₅₃/A ₂₀₃ ratio is useful for evaluating the contents of N forms. The structure of DOM and its fractions are important in affecting the contents of DON. Nitrate (NO₃-N) contributes to eutrophication, and thus cannot be ignored from studies of Erhai Lake sediment.     

Effects of iron-ore mining and processing on metal bioavailability in a tropical coastal lagoon

Background, aim, and scope

In water systems, water quality and geochemical properties of sediments determine the speciation of trace metals, metal transport, and sediment–water exchange, influencing metal availability and its potential effects on biota. Studies from temperate climates have shown that iron-ore mining and tailing wastewaters, besides being a source of trace metals, usually show high levels of dissolved ions and particulate suspended matter, thus having the potential of indirectly changing metal bioavailability. For the first time in the tropics, we identified the effects of iron-ore mining and processing on metal bioavailability in a coastal lagoon. With an extensive sampling scheme, we investigated the potential sources of metals; the links among metal levels in water, sediments, and invertebrates; and the contrasting effects on metal speciation and bioavailability.

Methodology

The metals Fe, Mn, Al, Cr, Zn, Cu, Ni, Pb, Cd, Hg, and As were measured in water, sediments (surface and profiles), and invertebrates from Mãe-Bá Lagoon and in the sites directly influenced by the mining operations (tailing dams and nearby rivers). In addition, samples from two other lagoons, considered pristine, were analyzed. The study area is located in the southeast of Brazil (Iron Quadrangle Region and a coastal area of Espírito Santo State). General water characteristics included pH, dissolved organic carbon, alkalinity, and anion composition. Water metal speciation was assessed by a speciation model (Chemical Equilibria in Aquatic Systems). Grain-size distribution, organic carbon, carbonate, and acid volatile sulfide (AVS) were determined in sediments. Statistical methods included comparison of means by Mann–Whitney test, ordination and correlation analyses, and analysis of regression for geochemical normalization of metals with grain size.

Results and discussion

The dissolved metal concentrations, the total metal levels in sediments, and the normalization based on the fine sediment fraction showed that the mining operations constitute potential sources of Fe, Mn, Cr, Cu, Ni, Pb, As, and Hg to Mãe-Bá Lagoon. However, trace metal availability was reduced because of increased pH, hardness, and sulfide content (356 μmol/g) in the sites influenced by the mining. The lagoon showed similar water chemistry as in the mining sites, with metal bioavailability further decreased by the presence of dissolved organic carbon and chloride. Although AVS levels in the lagoon were low (0.48–56 μmol/g), metal bioavailability was reduced because of the presence of organic matter. Metal levels in invertebrates confirmed the predicted low metal bioavailability in Mãe-Bá Lagoon. The lagoon was considered moderately contaminated only by Hg and As.

Conclusions

The iron-ore mining and processing studied here constitute potential sources of metal pollution into the tropical lagoon. Contrary to expectations, however, it also contributes to reducing the overall metal bioavailability in the lagoon.

Recommendations and perspectives

These findings are believed to be useful for evaluating metal exposure in a more integrated way, identifying not only the sources of pollution but also how they can affect the components involved in metal speciation and bioavailability in water systems, leading to new insights.