Invertebrates control metal/metalloid sequestration and the quality of DOC/DON released during litter decay in slightly acidic environments

Plant litter and organic sediments are a main sink for metals and metalloids in aquatic ecosystems. The effect of invertebrate shredder (a key species in litter decay) on metal/metalloid fixation by organic matter is described only under alkaline water conditions whereas for slightly acidic waters nothing can be found. Furthermore, less is known about the effect of invertebrate shredders on the quality of dissolved organic carbon (DOC) and nitrogen (DON) released during litter decay. We conducted an experiment to investigate the impact of invertebrate shredder (Gammarus pulex) on metal/metalloid fixation/remobilization and on the quality of DOC/DON released under slightly acidic water conditions. During decomposition of leaf litter, invertebrate shredder facilitated significantly the emergence of smaller particle sizes of organic matter. The capacity of metal fixation was significantly higher in smaller particles (POM 2,000?C63???m) compared to original leaf litter and litter residues. Thus, G. pulex enhanced metal fixation by organic partition of sediments by increasing the amount of smaller particle of organic matter in aquatic ecosystems. In contrast, the capacity of metal/metalloid fixation in the smallest fraction of POM (<63???m) was lower compared with leaf residues in treatment without invertebrates. Remobilization of metals and metalloids was very low for all measured elements. A significant effect of invertebrates on quantitative formation of DOC/DON was confirmed. The quality of released DOC/DON, which may affect metal/metalloid remobilization, was also significantly affected by invertebrate shredders (e.g., more carboxylates). Hence, invertebrate shredder enhanced significantly the fixation of metals/metalloids into POM in slightly acidic environments.     

Metal/metalloid fixation by litter during decomposition affected by silicon availability during plant growth

Organic matter is known to accumulate high amounts of metals/metalloids, enhanced during the process of decomposition by heterotrophic biofilms (with high fixation capacity for metals/metalloids). The colonization by microbes and the decay rate of the organic matter depends on different litter properties. Main litter properties affecting the decomposition of organic matter such as the nutrient ratios and the content of cellulose, lignin and phenols are currently described to be changed by silicon availability. But less is known about the impact of silicon availability during plant growth on elemental fixation during decay. Hence, this research focuses on the impact of silicon availability during plant growth on fixation of 42 elements during litter decay, by controlling the litter properties. The results of this experiment are a significantly higher metal/metalloid accumulation during decomposition of plant litter grown under low silicon availability. This may be explained by the altered litter properties (mainly nutrient content) affecting the microbial decomposition of the litter, the microbial growth on the litter and possibly by the silicon double layer, which is evident in leaf litter with high silicon content and reduces the binding sites for metals/metalloids. Furthermore, this silicon double layer may also reduce the growing biofilm by reducing the availability of carbon compounds at the litter surface and has to be elucidated in further research. Hence, low silicon availability during plant growth enhances the metal/metalloid accumulation into plant litter during aquatic decomposition.     

Effects of intense agricultural practices on heterotrophic processes in streams

In developed countries, changes in agriculture practices have greatly accelerated the degradation of the landscape and the functioning of adjacent aquatic ecosystems. Such alteration can in turn impair the services provided by aquatic ecosystems, namely the decomposition of organic matter, a key process in most small streams. To study this alteration, we recorded three measures of heterotrophic activity corresponding to microbial hydrolasic activity (FDA hydrolysis) and leaf litter breakdown rates with (k_c) and without invertebrates (k_f) along a gradient of contrasted agricultural pressures. Hydrolasic activity and k_f reflect local/microhabitat conditions (i.e. nutrient concentrations and organic matter content of the sediment) but not land use while k_c reflects land-use conditions. k_c, which is positively correlated with the biomass of Gammaridae, significantly decreased with increasing agricultural pressure, contrary to the taxonomic richness and biomass of Trichoptera and Plecoptera. Gammaridae may thus be considered a key species for organic matter recycling in agriculture-impacted streams.     

New methodological improvements in the Microtox® solid phase assay

The classic Microtox® solid phase assay (MSPA) based on the inhibition of light production of the marine bacteria recently renamed Aliivibrio fischeri suffers from various bias and interferences, mainly due to physico-chemical characteristics of the tested solid phase. To precisely assess ecotoxicity of sediments, we have developed an alternative method, named Microtox® leachate phase assay (MLPA), in order to measure the action of dissolved pollutants in the aqueous phase. Two hypotheses were formulated to explain the observed difference between MSPA and MLPA results: a real ecotoxicity of the solid phase or the fixation of bacteria to fine particles and/or organic matter. To estimate the latter, flow cytometry analyses were performed with two fluorochromes (known for their ability to stain bacterial DNA), allowing correction of MSPA measurements and generation of new (corrected) IC50. Comparison of results of MLPA with the new IC50 MSPA allows differentiating real ecotoxic and fixation effect in classic MSPA especially for samples with high amount of fines and/or organic matter.     

Influence of sediment acidification on the bioaccumulation of metals in Ruditapes philippinarum

Background, aim and scope

The influence of pH (range 6.5–8.5) on the uptake of Zn, Cd, Pb, Cu, Ni, Cr, Hg, and As by juveniles of the clam Ruditapes philippinarum was examined in order to understand whether variation in sediment pH has significant repercussions on metal bioaccumulation.

Materials and methods

Clams were exposed to sediments collected in three locations in the Gulf of Cadiz (Huelva, Guadalquivir and Bay of Cadiz) and to contaminated particles derived from an accidental mining spill in Spain.

Results

With a notable exception of metal Cd, the concentration of metals within clams significantly increased (p?<?0.1) when sediment pH was lowered by one or two units. Moreover, the magnitude of this effect was dependent on the type of sediment contamination.

Discussion

Lower pH increases metal solubility and reduces or invert the metal sorption of metals to sediments. Increases in free metal ions in water favors metal uptake by clams, hence pH is an important factor controlling the mobility of these metals within sediments and their subsequent bioaccumulation within biota. Although sediment-water exchange of Cd can increase with acidification, this excess may be counterbalanced by the presence of ligands in seawater preventing the uptake by organism. Besides chlorines, Cd has also an affinity with carbonates and other ligands present in sea water. These Cd-carbonate complexes may reduce the bioavailable to organisms.

Conclusions

These results highlight the potential implications of sediment acidification, either due to the storage excess of organic matter or to the forced capture of CO₂, on the increasing metal availability to benthic organisms.

Recommendations and perspectives

This kind of studies should be increased to address the influence of acidification in the behavior, bioavailability, toxicity, and risk assessment of contaminants associated with sediments either above sub-seabed geological formations in marine environments or in high enriched by organic matter in estuarine areas. Recently, the capture of CO₂ in marine environments has been approved and started; it is necessary to address the potential impacts associated with leakages or other events occurring during the procedure of injection and storage of CO2.     

Leaf litter leachates have the potential to increase lifespan, body size, and offspring numbers in a clone of Moina macrocopa

Leaf litter processing is one major pathway of the global organic carbon cycle. During this process, a variety of small reactive organic compounds are released and transported to the aquatic environment, and may directly impact aquatic organisms as natural xenobiotics. We hypothesize that different forest stockings produce different leachate qualities, which in turn, stress the aquatic communities and, eventually, separate sensitive from tolerant species. Particularly, leachates from coniferous trees are suspected to have strongly adverse impacts on sensitive species. We exposed individuals of a clone of the model organism, Moina macrocopa, to comparable concentrations (approximately 2 mM) of litter leachates of Norway spruce, Picea abies, Colorado blue spruce, Picea pungens, black poplar, Populus nigra, and sessile oak, Quercus petraea. The animals were fed ad libitum. The following life trait variables were recorded: growth, lifespan, and lifetime offspring. To identify, whether or not exposure to litter leachates provokes an internal oxidative stress in the exposed animals we measured the superoxide anion radical scavenging capacity via photoluminescence. Except of P. abies, exposure to the leachates reduced this antioxidant capacity by approximately 50%. Leachate exposures, except that of Quercus, increased body size and extended lifespan; furthermore, particularly the leachates of both Picea species significantly increased the offspring numbers. This unexpected behavior of exposed Moina may be based on food supplements (e.g., high carbohydrate contents) in the leachates or on yet to be identified regulatory pathways of energy allocation. Overall, our results suggest that the potentially adverse effects of litter leachates can be overruled by either bacterial-growth supporting fractions in the leachates or an internal compensation mechanism in the Moina individuals.     

A carbon budget of a small humic lake: an example of the importance of lakes for organic matter cycling in boreal catchments

Lakes play an important role in the cycling of organic matter in the boreal landscape, due to the frequently high extent of bacterial respiration and the efficient burial of organic carbon in sediments. Based on a mass balance approach, we calculated a carbon budget for a small humic Swedish lake in the vicinity of a potential final repository for radioactive waste in Sweden, in order to assess its potential impact on the environmental fate of radionuclides associated with organic matter. We found that the lake is a net heterotrophic ecosystem, subsidized by organic carbon inputs from the catchment and from emergent macrophyte production. The largest sink of organic carbon is respiration by aquatic bacteria and subsequent emission of carbon.dioxide to the atmosphere. Although the annual burial of organic carbon in the sediment is a comparatively small sink, it results in the build-up of the largest carbon pool in the lake. Hence, lakes may simultaneously disperse and accumulate organic-associated radionuclides leaking from a final repository.     

Influence of algal organic matter on metal accumulation in adjacent sediments of aquaculture from a tropical coast region

The rapid development of coastal aquaculture in recent decades has led to excessive discharge of organic matter and nutrients into surrounding waters, which could result in eutrophication and potentially affect metal cycling. In our study, the influence of algal organic matter on metal accumulation was examined in three coastal sediment cores taken from a tropical region, Hainan Island, China. Overall, metal pollution adjacent to aquaculture ponds remained at low levels on the coast, except Zn, Cd, and Sn were moderately to highly enriched in the Dongjiao sediments. The δ¹³C values and the atomic C/N ratios indicated a major contribution of phytoplankton to sedimentary organic matter at the Dongjiao site. Moreover, both the algae-derived organic matter and effluent nitrogen were significantly associated with the enriched Zn, Cd, and Sn, suggesting that nutrient-induced phytoplankton growth and its organic matter may act as a “biological pump” to enhance the accumulation of metals. Wastewater treatment for aquaculture ponds should include the control of algal organic matter.

     

An attempt to assess the relevance of flood events—biomarker response of rainbow trout exposed to resuspended natural sediments in an annular flume

There is a consensus within the scientific community that sediments act as a long-term sink for a variety of organic and inorganic pollutants, which, however, can re-enter the water column upon resuspension of deposited material under certain hydraulic conditions such as flood events. Within the implementation of the European Water Framework Directive, it is important to understand the potential short- and long-term impact of suspended particulate matter (SPM)-associated contaminants on aquatic organisms as well as the related uptake mechanisms for a sound risk assessment. To elucidate the effects of sediment-bound organic pollutants, such as polycyclic aromatic hydrocarbons (PAHs), rainbow trout (Oncorhynchus mykiss) were exposed to three resuspended natural sediments with different contamination levels. Physicochemical parameters including dissolved oxygen concentration, pH and temperature, total PAH concentration in sediments and SPM as well as different biomarkers of exposure in fish (7-ethoxyresorufin O-deethylase activity, biliary PAH metabolites, micronuclei, and lipid peroxidation) were measured following seven days of exposure within an annular flume, a device to assess erosion and deposition processes of cohesive sediment. Concentrations of PAHs in SPM remained constant and represented the different contamination levels in the un-suspended sediments. Significant differences in bile metabolite concentrations as well as in 7-ethoxyresorufin O-deethylase induction compared to control experiments (untreated animals and animals that were exposed in the annular flume without sediment) were observed for all exposure scenarios. The ratio between 1-hydroxypyrene in bile from fish exposed to the three different contamination levels was 1.0:3.6:10.7 and correlated well with (1) the ratio of pyrene concentrations in corresponding sediments which was 1.0:3.1:12.7 and (2) with the ratio of particle-bound pyrene in SPM which was 1.0:2.7:11.7. In contrast, hepatic lipid peroxidation and micronuclei formation represented the different contamination levels less conclusive. The results of this study clearly demonstrate that firmly bound PAH from aged sediments can become bioaccessible upon resuspension under flood-like conditions and are readily absorbed by aquatic organisms such as rainbow trout. Associated short-term effects were clearly documented and possible adverse long-term impacts due to genotoxicity are likely to follow.     

北运河表层沉积物对重金属Cu、Pb、Zn的吸附

首先分析了北运河6个采样点表层沉积物中重金属含量及相关基本特征。通过实验室模拟实验,利用分配系数Kd评价沉积物对重金属Cu、Pb、Zn的吸附特性,进一步考察了水体pH变化和有机质对重金属在北运河沉积物上吸附的影响。结果表明,沉积物中重金属的含量顺序为Zn>Cu>Pb,去除有机质后,沉积物对重金属的吸附能力显著降低,但各采样点中的重金属含量,沉积物对重金属吸附能力,以及沉积物中的有机质含量并没有明显相关性,这可能是因为不同采样点中有机质种类与结构不同导致的。总之,北运河沉积物对Pb有很强的吸附能力,其次是Cu和Zn,而且,Cu、Zn、Pb的吸附量随着pH的升高逐渐增大,水体pH值对于Zn的吸附影响更大。     

不同粒径泥沙理化特性对磷吸附过程的影响

以北京大兴南海子湖表层沉积物为研究对象,测试分析了0.147～0.246 mm(细砂)、0.074～0.147 mm(极细砂)、0.0385～0.0740 mm(粉粒)和<0.0385 mm(粉粒粘粒混合物)4种粒径泥沙对磷的吸附行为,并采用相关分析及逐步回归分析探讨不同粒径沉积物中有机质(OM)、Fe、Al、Ca、Mn和TP含量对磷吸附过程的影响。结果表明,二级动力学方程和Langmuir模型能较好地描述南海子不同粒径泥沙的吸附动力学及等温吸附过程(R2>0.90)。粒径对单位质量泥沙吸附磷量具有明显影响,粉粒粘粒混合物>粉粒>细砂>极细砂。总体上,泥沙有机质(OM)、TP、Fe、Al、Ca和Mn含量随粒径的减小而增大,且粘粒对其影响较大。不同粒径泥沙(OM)、Fe、Al、Ca和Mn含量之间存在极显著正相关关系(P<0.01),且均对单位质量泥沙最大吸附量(Xm)和饱和吸附量(Cse)具有正效应,其中Al含量对该参数的影响更为显著。这说明泥沙对磷的吸附行为可能受到粒径和化学成分的共同影响。     

Agro-industrial wastes as effective amendments for ecotoxicity reduction and soil health improvement in aided phytostabilization

Aided phytostabilization is a technology that uses metal tolerant plants and organic and/or inorganic amendments to reduce soil metal bioavailability, while improving soil health. Our objective was to determine the effects of the application of amendments [sheep manure (SHEEP), poultry litter (POULTRY), cow slurry (COW), and paper mill sludge mixed with poultry litter (PAPER)], together with the growth of a metallicolous Festuca rubra L. population, on (i) chemical and microbial indicators of soil health and (ii) soil ecotoxicity, during the aided phytostabilization of a Zn/Pb contaminated mine soil. Amendment application led to an increase in soil pH, organic matter content, and inorganic salts, resulting in a decrease in Pb and Zn CaCl₂-extractable concentrations in soil, which, in turn, contributed to lower ecotoxicity and a stimulation of plant growth and soil microbial communities. The factor most affecting the metal extractability was probably soil pH. POULTRY was the best amendment in terms of increasing plant growth, chlorophylls content, and soil microbial biomass and activity, but resulted in higher levels of phytoavailable Pb and Zn. SHEEP and PAPER were more effective at reducing metal CaCl₂-extractability and, consequently, led to lower values of metal accumulation in plant tissues, thereby reducing the risk of metals entering into the food chain. When combined with the application of organic amendments, the metallicolous F. rubra population studied here appears an excellent candidate for aided phytostabilization. Our results indicate that the application of organic amendments is essential for the short-term recovery of highly contaminated metalliferous soils during aided phytostabilization.     

Cu sorption on Phragmites australis leaf and stem litter: a kinetic study

Decaying organic matter plays an important role in the cycling of metals in wetland ecosystems. Sorption kinetics of Cu(II) on Phragmites australis leaf and stem litter were studied. Fresh leaf and stem litter was sampled from a surface flow wetland at the end of the growing season. The effect of decomposition stage was studied with litter that had been decomposing for a period of 5 months. The Lagergren pseudo-first-order model, the pseudo-second-order model, the Elovich equation and two diffusion models based on spherical intra-particle diffusion were fitted to the experimental data. The sorption capacity was significantly affected by the decomposition of the litter. The sorption process was best described by the pseudo-second-order kinetics (R(2) approximately 0.99) but the rate constant was strongly dependent on the initial Cu concentration. The intra-particle diffusion model fitted the data only slightly less (R(2)>0.95) than the pseudo-second-order model. A theoretical comparison revealed that the good fit with the pseudo-second-order kinetics could be indicative of intra-particle diffusion. Sorption kinetics observed for the leaf and stem litter at different metal concentrations showed a fast initial sorption followed by a slow sorption phase.     

Heavy metal distribution in an urban wetland impacted by combined sewer overflow

The heavy metal content and distribution in an urban wetland affected by combined sewer overflow (CSO) discharge during dry conditions was evaluated. Metals identified in the CSO discharge were also measured upstream and downstream of the CSO. Metals were detected in the acid-extractable fraction of the wetland sediments and the roots of Phragmites australis plants. Sediment from the banks of a pool created by the CSO, and from a clay bed upstream were found to be moderately contaminated with Cu, Pb and Zn. Micro X-ray fluorescence (μ-XRF) of Phragmites roots from the CSO banks showed a correlation in the spatial distribution of Fe and Mn, attributed to the formation of mineral plaques on the root surface. Micro X-ray absorption near edge spectroscopy (μ-XANES) revealed that Cu and Zn were complexed with the organic ligands phytate and cysteine. The findings indicated that continuous discharge from the CSO is a source of heavy metals to the wetland. Metals bound to sediments are susceptible to remobilization and subsequent transport, whereas those associated with Phragmites roots may be more effectively sequestered. These observations provide insight into the behavior of heavy metals in urban areas where CSOs discharge into wetlands.     

The impact of vegetation on sedimentary organic matter composition and PAH desorption

Relationships between sedimentary organic matter (SOM) composition and PAH desorption behavior were determined for vegetated and non-vegetated refinery distillate waste sediments. Sediments were fractionated into size, density, and humin fractions and analyzed for their organic matter content. Bulk sediment and humin fractions differed more in organic matter composition than size/density fractions. Vegetated humin and bulk sediments contained more polar organic carbon, black carbon, and modern (plant) carbon than non-vegetated sediment fractions. Desorption kinetics of phenanthrene, pyrene, chrysene, and C₃-phenanthrene/anthracenes from humin and bulk sediments were investigated using Tenax^® beads and a two-compartment, first-order kinetic model. PAH desorption from distillate waste sediments appeared to be controlled by the slow desorbing fractions of sediment; rate constants were similar to literature values for k_slow and k_{very slow}. After several decades of plant colonization and growth (Phragmites australis), vegetated sediment fractions more extensively desorbed PAHs and had faster desorption kinetics than non-vegetated sediment fractions.     

Assessment of pollution in road runoff using a Bufo viridis biological assay

Road runoff is a major source of environmental pollution, significantly threatening nearby aquatic habitats. Chemical analyses indicate high pollutant concentrations in the road’s “first flush”, but bioassays are more advantageous for addressing the cumulative effects of the numerous pollutants within the runoff. We used Bufo viridis embryos and larvae to assess the toxicity of road runoff from two major highways in Israel. We show, for the first time, that exposure to midseason runoff not only has an adverse effect on growth and development rates of B. viridis larvae but can also lead to increased rates of morphological deformations. Seasonal first flushes, despite having higher metal concentrations, did not adversely affect the toad larvae, apparently due to a counter effect of organic matter that potentially served as a supplementary energy resource. Road runoff can be a major cause for a qualitative decrease in the quality of aquatic habitats threatening amphibians in Israel.     

Sediments as a sink for UV filters and benzotriazoles: the case study of Upper Iguaçu watershed,Curitiba (Brazil)

Ingredients in home and personal care products, including UV filters and benzotriazoles, are high production volume chemicals extensively used in our daily life, despite several studies revealed their potential eco-toxicity and endocrine-disrupting capacity. Due to some features, such as high lipophilicity, low degradability, and persistence of many of these compounds, sediments can be considered a sink for them in the aquatic environment. In the present study, nine organic UV filters and three benzotriazoles were investigated for the first time in sediments from four urban rivers in Brazil. The contaminants were analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The results revealed that octocrylene (OC), etylhexyl-methoxycinnamate (EHMC), benzophenone-3 (oxybenzone, BP3), and benzotriazole (BZT) were the predominant compounds adsorbed on the sediments, with concentrations ranging from 5.6 to 322.2 ng g⁻¹ dry weight. The results reported in this work constitute the first data on the accumulation of polar benzotriazoles and lipophilic organic UV filters in sediments from Brazil.

     

Effects of metals on feeding rate and digestive enzymes in Gammarus fossarum: An in situ experiment

The feeding activity and afterward the assimilation of the products resulting of the food digestion, allow organisms to obtain energy useful for growth, maintenance and reproduction. These biological parameters may be studied to assess the impact of contaminants on the energy metabolism of organisms, which could induce potential effects at an individual level. The studied species was an amphipod Gammarus fossarum, which has a high ecological relevance since it is widespread in European streams and plays a major role in the breakdown of leaf litter. Thus some G. fossarum were transplanted in four sites of a river characterized by metal contamination (Amous River, France). The following parameters were studied: digestive enzymes activities (esterase, β-glucosidase, β-galactosidase, amylase and endoglucanase), feeding rate, metal bioaccumulation and survival. Results showed a strong relationship between digestive enzymes activities, feeding rate and metal contents.     

Can behavioural responses of Lumbriculus variegatus (Oligochaeta) assess sediment toxicity? A case study with sediments exposed to acid mine drainage

The São Domingos mine (Portugal) is, potentially, a good site for ecotoxicological studies, due to a pH and metal gradient of acid mine drainage. In this study, the toxicity of several mine sediments was evaluated using the aquatic oligochaete Lumbriculus variegatus as a test organism. Our hypothesis was that exposure to contaminated sediments would cause behavioural early warning responses in L. variegatus. Five sites, with pH ranging from 2.5 to 6.5, and with associated metals, were investigated. The results showed poor sediment quality in most of the collected sediments and Fe, S and As were the dominant elements in the samples. High mortalities were observed, ranging from 32.6 to 100%, indicating severe contamination. The collected sediments did not support good L. variegatus growth and significantly changed its behaviour. Early warning responses consisted of decreased locomotion and decreased peristaltic movements. A behaviour inhibition will affect the ecosystem balance by limiting the organisms' ability to avoid capture, which leads to a higher risk of predation.     

Metal accumulation in intertidal litter through decomposing leaf blades, sheaths and stems of Phragmites australis

Metal contents of decomposing leaf blades, leaf sheaths and stems of common reed (Phragmites australis) were monitored by a litter bag method on the sediment of an intertidal brackish marsh in the Scheldt estuary (The Netherlands). On monthly intervals, two litter bags were retrieved from the marsh during 9 months for both leaf blades and sheaths and during 16 months for stems. All samples were dried, weighed and analysed for ash and Cd, Cu, Cr, Ni, Pb and Zn contents. Most concentrations increased considerably during the decomposition. Generally, also a very important net metal inflow into the litter bags could be observed. The inflow was highest for leaf blades. High correlations between ash contents and metal concentrations for leaf blades suggest that the increase of leaf blade metal contents can be due to physicochemical sorption of dissolved metals and an important infiltration of mud particles, which were not removed by rinsing the leaf blades with distilled water preceding the analyses. For stems, smaller amounts of inflowing ash and even outflowing ash amounts were found, which suggests that inflow of inorganic particles is not the major factor determining metal accumulation by stems on medium term. Ergosterol concentrations in stem tissue however proved to be correlated with metal contents, which suggests a significant role of fungal litter colonizers in metal accumulation. For leaf sheaths, the effects of physicochemical sorption, infiltration of mud particles and incorporation by microbial litter colonizers do not seem to be as pronounced as for stems and leaf blades.