Humic substances

GOALS, SCOPE AND BACKGROUND: Changing environmental conditions and handling stress are well known to cause chronic or acute stress situations in fish with subsequent infections. These requires a therapy by means of antibiotics and chemicals. In contrast to the huge number of pathogens, only a few substances are permitted for application as therapeutics in German aquaculture. Hence, there emerges an urgent need for highly effective and residueless alternatives. MAIN FEATURES: The prophylactic stimulation and training of the defense system of fish by alternative approaches becomes increasingly necessary. One approach is the application of dissolved humic substances (HS) of natural or artificial origin. For example, there exist several reports on the positive effect of HS to fishes. These effects shall be considered in detail. Furthermore, the impact of HS on the constitution of parasites and pathogens will be displayed. The reports on this issue are diverse, if not inconsistent. We try to shed some light on these discrepancies. The last aspect covered by this review is the outdated paradigm that calcium ions act as antidotes. In the presence of HS, even the opposite effect may occur. APPROACH: To overcome old paradigms on HS and their potential interactions with fish and fish parasites, we reviewed recent international literature, as well as 'grey' literature. We also include results from own former and ongoing studies. RESULTS AND DISCUSSION: HS are able to increase the physiological condition of the individuals and to reduce adverse physiological and histological consequences caused by stress; the mechanism behind remains obscure. HS detoxify heavy metals and organic pollutants. Damages caused by several fish pathogens, such as bacteria and parasites, can be repaired more quickly in the presence of HS. Some parasites--mainly fungi--appear to be directly affected by HS. Comparing the fungicidal effects of HS from various sources, evidence is increasing that the aliphatic moiety may be the effective structures. However, further research is necessary to relate more physiological and anti-pathogenic effects to the chemical characteristics of HS. CONCLUSIONS: HS are not real alternatives to strong traditional therapeutics. However, they show different advantages in repairing secondary, stress induced damages in fish. The ecophysiological relevance of HS in either aquatic systems or aquaculture is getting conspicuously. PERSPECTIVES: The lack of therapeutic and antiparasitic substances in aquaculture requires new strategies and ways of thinking. The search for alternatives to the 'traditional' chemical therapeutics calls for the intensive research. Inevitably, this search will lead to an intensive contemplation on HS as 'health promoting substances' and/or even therapeutics. Basic research is needed to detect the functional groups of the HS responsible for the effects observed. Health promoting effects of first investigations made in vitro to affect pathogens via application of HS and several field studies with HS raises hopes for a broader utilisation of HS to reduce stress consequences in fish and fish pathogens residuelessly.     

Environmental signals: synthetic humic substances act as xeno-estrogen and affect the thyroid system of Xenopus laevis

According to outdated paradigms humic substances (HS) are considered to be refractory or inert that do not directly interact with aquatic organisms. However, they are taken up and induce biotransformation activities and may act as hormone-like substances. In the present study, we tested whether HS can interfere with endocrine regulation in the amphibian Xenopus laevis. In order to exclude contamination with phyto-hormones, which may occur in environmental isolates, the artificial HS1500 was applied. The in vivo results showed that HS1500 causes significant estrogenic effects on X. laevis during its larval development and results of semi-quantitative RT-PCR revealed a marked increase of the estrogenic biomarker estrogen receptor mRNA (ER-mRNA). Furthermore, preliminary RT-PCR results showed that the thyroid-stimulating hormone (TSHbeta-mRNA) is enhanced after exposure to HS1500, indicating a weak adverse effect on T3/T4 availability. Hence, HS may have estrogenic and anti-thyroidal effects on aquatic animals, and therefore may influence the structure of aquatic communities and they may be considered environmental signaling chemicals.     

Natural dissolved humic substances increase the lifespan and promote transgenerational resistance to salt stress in the cladoceran <Emphasis Type="Italic">Moina macrocopa</Emphasis>

Purpose  

Evidence has accumulated that humic substances (HS) are not inert biogeochemicals. Rather, they cause stress symptoms and may modulate the life history of aquatic organisms. Nevertheless, it is still not clear how HS interact with additional stressors and if their effects are transgenerational. We tested the interactive effects of HS and salt to cladocerans, discussing their consequences for the persistence in fluctuating environments, such as coastal lagoons.     

Natural Organic Matter Differently Modulates Growth of Two Closely Related Coccal Green Algal Species (6 pp)

Background

and Aim. Humic substances (HS) comprise the majority of dead and living organic carbon, including organisms. In the environment, they are considered to be chemically inert or at least refractory. Recent papers, however, show that HS (including natural organic matter – NOM, isolated by reverse osmosis) are natural chemicals which interact with aquatic organisms. They are taken up and cause a variety of stress defense reactions which are well known from man-made chemicals. These reactions include chaperon activation, induction and modulation of biotransformation enzymes, or induction of antioxidant defense enzymes. One specific reaction with freshwater plants is the reduction of photosynthetic oxygen release. In this contribution, we compare the susceptibilities (cell yield) of two closely related coccal green algae, Monoraphidium convolutum and M. minutum, towards various NOM isolates.

Methods

Cultures of M. convolutum and M. minutum were obtained from the algal collection of the Leibniz Institute of Freshwater Ecology and Inland Fisheries, Berlin, and from the Culture Collection of Algae, Göttingen, and maintained in a common medium. The cultures were non-axenic. The algae were exposed to 5 mg L-1 DOC of each humic material, an environmentally realistic concentration. Cell numbers were counted microscopically in Neugebauer cuvettes in 5 replicates on days 1, 4, 7, 10, 14, and 21.

Results and Discussion

Almost all NOM isolates modulated the growth of the algae. Only the NOM of a Norwegian raised peat bog lake did not reveal any significant effect with M. convolutum. In general, the results with two algal species are by no means uniform. For instance, Suwannee River NOM causes a decrease in cell density with M. minutum, but temporarily stimulates the growth of M. convolutum. The opposite applies to Aurevann NOM: Growth increase in M. minutum, but a bi-phasic response in M. convolutum. Different responses of both Monoraphidium species must be attributed to intrinsic factors of the algae rather than only to chemical features of the exposed materials, because the exposures were identical with both algal species. The reduction in growth yields can be explained as a herbicide-like mode of action that affects the photosystem II most prevalently. The growth promoting effect remains somewhat obscure. It may be due to (1) an increase in bioavailability of some trace nutrients in the presence of HS, (2) the release of some growth promoting substances by microbial or photochemical processing of the humic materials, and (3) a hormetic effect upon the exposure of HS. Hormesis means stimulation of organisms or metabolic activities when exposed to noxes in low concentrations. However, it is still open to discussion why the growth promotion only applies to one or the other, but not simultaneously to both Monoraphidium species.

Conclusion

and Perspectives. Exposure of the closely related coccal green algal species to humic material changes their growth characteristics. Since the reactions are not consistent within the two species and the various humic materials, it seems that the less sensitive species is favored by HS exposure. The environmental relevance, however, is subject to future studies.     

DOC removal paradigms in highly humic aquatic ecosystems

Background, aim, and scope  Dissolved humic substances (HS) usually comprise 50–80% of the dissolved organic carbon (DOC) in aquatic ecosystems. From a trophic and biogeochemical perspective, HS has been considered to be highly refractory and is supposed to accumulate in the water. The upsurge of the microbial loop paradigm and the studies on HS photo-degradation into labile DOC gave rise to the belief that microbial processing of DOC should sustain aquatic food webs in humic waters. However, this has not been extensively supported by the literature, since most HS and their photo-products are often oxidized by microbes through respiration in most nutrient-poor humic waters. Here, we review basic concepts, classical studies, and recent data on bacterial and photo-degradation of DOC, comparing the rates of these processes in highly humic ecosystems and other aquatic ecosystems. Materials and methods  We based our review on classical and recent findings from the fields of biogeochemistry and microbial ecology, highlighting some odd results from highly humic Brazilian tropical lagoons, which can reach up to 160 mg C L⁻¹. Results and discussion  Highly humic tropical lagoons showed proportionally lower bacterial production rates and higher bacterial respiration rates (i.e., lower bacterial growth efficiency) than other lakes. Zooplankton showed similar δ¹³C to microalgae but not to humic DOC in these highly humic lagoons. Thus, the data reviewed here do not support the microbial loop as an efficient matter transfer pathway in highly humic ecosystems, where it is supposed to play its major role. In addition, we found that some tropical humic ecosystems presented the highest potential DOC photo-chemical mineralization (PM) rates reported in the literature, exceeding up to threefold the rates reported for temperate humic ecosystems. We propose that these atypically high PM rates are the result of a joint effect of the seasonal dynamics of allochthonous humic DOC input to these ecosystems and the high sunlight incidence throughout the year. The sunlight action on DOC is positive to microbial consumption in these highly humic lagoons, but little support is given to the enhancement of bacterial growth efficiency, since the labile photo-chemical products are mostly respired by microbes in the nutrient-poor humic waters. Conclusions  HS may be an important source of energy for aquatic bacteria in humic waters, but it is probably not as important as a substrate to bacterial growth and to aquatic food webs, since HS consumption is mostly channeled through microbial respiration. This especially seems to be the case of humic-rich, nutrient-poor ecosystems, where the microbial loop was supposed to play its major role. Highly humic ecosystems also present the highest PM rates reported in the literature. Finally, light and bacteria can cooperate in order to enhance total carbon degradation in highly humic aquatic ecosystems but with limited effects on aquatic food webs. Recommendations and perspectives  More detailed studies using C- and N-stable isotope techniques and modeling approaches are needed to better understand the actual importance of HS to carbon cycling in highly humic waters.     

Enhanced growth and reproduction of Caenorhabditis elegans (Nematoda) in the presence of 4-nonylphenol

The nematode Caenorhabditis elegans was exposed over a whole fife-cycle (72 h) to several concentrations of 4-nonylphenol (NP; nominal concentrations: 0-350 microg/l). Growth and reproduction of C. elegans were enhanced at NP concentrations of 66 and 40 microg/l, respectively, with effects showing dose-response relationships. These stimulatory effects might be of ecological relevance in benthic habitats, where organisms can be exposed to high concentrations of NP.     

Competition between alga (Pseudokirchneriella subcapitata), humic substances and EDTA for Cd and Zn control in the algal assay procedure (AAP) medium

The chemical speciation of trace metals in natural waters has important implications for their biogeochemical behavior. Trace metals are present in natural waters as dissolved species and associated with colloids and particles. The complexation of one trace metal (Cd and Zn at 200 and 390 microg/l respectively) with a green alga Pseudokirchneriella subcapitata in colloid-free algal culture medium and in presence of colloidal humic substances (HS) is presented. The influence of the nature of colloids was also addressed using three "standard" HS: fulvic acid (FA) and, soil (SHA) and peat humic acids (PHA). The chemical speciation model, MINTEQA2, was used to simulate the influence of pH and standardized culture medium on metal association with humic substances. The model was successfully modified to consider the differences in the metal complexation with fulvic (FA) and humic acids (HA). The deviations of concentrations of metals associated with HS between experimental results and model predictions were within a factor of approximately 2. The results of speciation model highlight the influence of the experimental conditions (pH, EDTA) used for alga bioassay on the behavior of Cd and Zn. The computed speciation suggests working with a pH buffered/EDTA-free mixture to avoid undesirable competition effects. The behavior of Cd and Zn in solution is more strongly influenced by HS than by alga. Metal-HS associations depend on metal and humic substance nature and concentration. Cd is complexed to a higher extent than Zn, in particular at larger HS concentration, and the complexation strength is in the order FA相似文献   

Surfactive stabilization of multi-walled carbon nanotube dispersions with dissolved humic substances

Soil humic substances (HS) stabilize carbon nanotube (CNT) dispersions, a mechanism we hypothesized arose from the surfactive nature of HS. Experiments dispersing multi-walled CNT in solutions of dissolved Aldrich humic acid (HA) or water-extractable Catlin soil HS demonstrated enhanced stability at 150 and 300 mg L⁻¹ added Aldrich HA and Catlin HS, respectively, corresponding with decreased CNT mean particle diameter (MPD) and polydispersivity (PD) of 250 nm and 0.3 for Aldrich HA and 450 nm and 0.35 for Catlin HS. Analogous trends in MPD and PD were observed with addition of the surfactants Brij 35, Triton X-405, and SDS, corresponding to surfactant sorption maximum. NEXAFS characterization showed that Aldrich HA contained highly surfactive domains while Catlin soil possessed a mostly carbohydrate-based structure. This work demonstrates that the chemical structure of humic materials in natural waters is directly linked to their surfactive ability to disperse CNT released into the environment.     

Wastewater discharges may be most hazardous to fish during winter

Winter Stress Syndrome (WSS) is a condition of severe lipid depletion in fish brought on by external stressors in combination with normal reductions in feeding and activity during cold weather. Fish can develop this syndrome in response to chemical stressors such as water pollutants, or biological stressors such as parasites. Substantial mortality can result, potentially changing year-class strength and population structure of the affected species, and altering community-level ecological interactions. Aquatic contaminants should be evaluated in the context of seasonal metabolic changes that normally occur in test organisms. WSS could be an important, but as yet unquantified, cause of mortality in many circumstances. Wastewater discharges may pose a greater toxic threat to fish during winter than at other times of the year. A comprehensive protocol for aquatic hazard assessment should include testing for WSS.     

The double-edged sword of humic substances: contrasting their effect on respiratory stress in eastern rainbow fish exposed to low pH

High amounts of humic substances (HS) are commonly found in natural acidic waterways and have been suggested to offer some protection against low pH. This study investigated the ability of HS to decrease respiratory stress in eastern rainbowfish (Melanotaenia splendida splendida) exposed to decreases in pH (range of 7–3.5) in soft and hard water. Repeated measures ANOVA revealed a significant difference in respiration (time taken for ten operculum movements) between pH and HS treatments, with a significant interaction between pH and HS present in 5/6 trials. Respiratory stress was shown to increase with increasing acidity, but significantly decreased in treatments with HS (10 and 20 mg/L) compared to those without. The fish exposed to pH treatments without HS also displayed increased hyperactivity, larger operculum movements and increased mucous production. Increased morbidity was shown in HS treatments at pH 3.5 (soft water) and at pH 4 (hard water) compared to treatment without HS. This indicates that HS is helpful in ameliorating the effects of decreased pH on respiration at sublethal pH levels; however, as pH decreases further, it seems that HS increases the toxicity (morbidity) of the low pH.     

Ecological risk of pesticide residues in the British Columbia environment: 1973–2012

An updated ecological risk assessment was conducted to re-evaluate and review the overall risk of pesticide residues to certain aquatic life. The focus was the impact on offsite non-target, freshwater organisms of pesticide operational sprays in British Columbia from 1973 until 2012. The values of risk quotients for pesticides of selected indicator organisms were determined to measure the effect. When compared with organophosphorus, carbamate, and other miscellaneous pesticides, this risk assessment analysis suggests that the historical use of persistent and highly toxic organochlorine pesticides posed, and continue to pose, a deleterious ecological risk. The risk is both short-term acute and long-term sub-acute, chronic toxicity to offsite, non-target aquatic invertebrates and juvenile salmonid fish. Data indicated that these organisms were, and remain, subjected to harmful effects of pesticide residues to varying degrees. Most vulnerable were, and also are, benthic organisms inhabiting bottom sediments. This substrate is the natural sink for persistent pesticide residues, predominantly organochlorine pesticides from historical use, as well as dioxins, furans, and polycyclic aromatic hydrocarbons from wood preservatives, and other sources. Environment Canada's main aquatic protection strategy was a 10 metre no-treatment buffer zone, augmented with an additional appropriate setback along shorelines of fishery and wildlife resource-sensitive water bodies. This study discusses why this guideline was necessary, useful and effective, but was only partially successful. The physical-chemical properties of pesticide residues, from either an individual compound or different compounds in combination, also influence the nature of biological impacts on non-target, aquatic organisms. Few studies have been conducted in British Columbia aquatic environments to investigate the significance of this aspect.     

Effects of photodegradation of dissolved organic matter on the binding of benzo(a)pyrene

Dissolved organic matter (DOM) in natural waters can bind various organic pollutants, and the affinity of this binding is strongly influenced by the chemical characteristics of the DOM and water pH. This study examined the effects of photochemically induced alteration of the DOM's chemical properties and water pH on the binding of benzo(a)pyrene (BaP). Time- and pH-series of solar-simulated irradiations were performed on a natural water sample and aqueous DOM solutions prepared from aquatic and soil humic substances. The binding affinity of BaP, expressed as a partition coefficient of a compound to DOM, decreased substantially after the DOM samples were irradiated over environmentally relevant radiation doses and pH ranges. The lowering of the pH due to the photoproduction of acidic products often partly offsets the reduction of the binding affinity caused by direct photoalteration of the DOM's chemical structure. The decrease of the binding affinity, after correction for the photoinduced pH change, was positively correlated with the decrease in the molecular weight and the aromaticity of the DOM in the course of irradiation. Increasing O(2) abundance accelerated the decrease of the binding affinity as a result of enhanced DOM photodegradation. Visible light played a more important role in reducing the molecular weight and aromaticity of the DOM than in reducing the content of dissolved organic carbon (DOC) via photoremineralization while the reverse was true for UV radiation, indicating that photochemical reduction of the binding affinity may occur in natural waters at depths greater than UV radiation can reach. A decrease of the affinity of DOM for binding BaP will increase the free dissolved fraction of BaP and thus its availability and toxicity to aquatic organisms. The results from this study may have similar implications for organic pollutants other than BaP.     

纳米材料的水生态毒理学研究进展

纳米材料特殊的理化特性,使它们被广泛地应用到各个生活领域中,但纳米材料给人们生活带来巨大改变的同时,其对水环境引起的负面效应也引起了人们广泛的关注.纳米材料可通过多种途径进入水体,对水生生物产生毒理效应,其生态学影响不可忽视.目前,还很缺乏对纳米材料的水生态毒理学研究,众多不确定的生态安全性问题还有待更深入的研究.总结了国内外现有的相关研究,简要综述了纳米材料的水环境行为、水生态毒理学研究现状,分析了该研究领域的未来需要.     

水源水中摇蚊幼虫的孳生与生态控制

摇蚊幼虫(红虫)在城市供水系统中的出现,成为困扰水厂正常生产运行的又一水处理难题.首先对其生理特性与环境因子之间的关系进行了论述,然后从生态学角度出发,利用生态群落中的食物链关系,分析了富营养化水体中摇蚊幼虫大量孳生的原因.在此基础上提出了利用合理的生物操纵技术,通过鱼类与水生生物间的"下行效应",以达到恢复生态平衡并控制摇蚊幼虫孳生为目的的生态治理方案.     

Microplastics in aquatic environment: characterization,ecotoxicological effect,implications for ecosystems and developments in South Africa

Microplastics are small-size plastic piece scales (particles <?5 mm) in sediments and waters which interact with environment and organisms by various means. Microplastics are becoming a universal ecological concern since they may be a source of hazardous chemicals to marine organisms and environments. Recent research suggests microplastics could enable the transfer of hydrophobic aquatic pollutants or chemical additives to biota. Even though microplastic presence and interactions are recently being detected in marine and freshwater systems, the fate of microplastics is still very poorly understood. This literature review is a summary of the sources and transport of microplastics, their interactions with toxic chemicals and the methodologies for chemical quantification and characterization of microplastics. The environmental outcome and impact of microplastics in wastewater treatment plants were assessed as well as the trends and update on microplastic research in the South African aquatic ecosystem.

     

Assessment of general condition of fish inhabiting a moderately contaminated aquatic environment

The assessment of general condition of fish in the moderately contaminated aquatic environment was performed on the European chub (Squalius cephalus) caught in September 2009 in the Sutla River in Croatia. Although increases of the contaminants in this river (trace and macro elements, bacteria), as well as physico-chemical changes (decreased oxygen saturation, increased conductivity), were still within the environmentally acceptable limits, their concurrent presence in the river water possibly could have induced stress in aquatic organisms. Several biometric parameters, metallothionein (MT), and total cytosolic protein concentrations in chub liver and gills were determined as indicators of chub condition. Microbiological and parasitological analyses were performed with the aim to evaluate chub predisposition for bacterial bioconcentration and parasitic infections. At upstream river sections with decreased oxygen saturation (～50 %), decreased Fulton condition indices were observed (FCI: 0.94 g?cm^?3), whereas gonadosomatic (GSI: 2.4 %), hepatosomatic (HSI: 1.31 %), and gill indices (1.3 %) were increased compared to oxygen rich downstream river sections (dissolved oxygen ～90 %; FCI: 1.02 g?cm^?3; GSI: 0.6 %; HIS: ～1.08 %; gill index: 1.0 %). Slight increase of MT concentrations in both organs at upstream (gills: 1.67 mg?g^?1; liver: 1.63 mg?g^?1) compared to downstream sites (gills: 1.56 mg?g^?1; liver: 1.23 mg?g^?1), could not be explained by induction caused by increased metal levels in the river water, but presumably by physiological changes caused by general stress due to low oxygen saturation. In addition, at the sampling site characterized by inorganic and fecal contamination, increased incidence of bacterial bioconcentration in internal organs (liver, spleen, kidney) was observed, as well as decrease of intestinal parasitic infections, which is a common finding for metal-contaminated waters. Based on our results, it could be concluded that even moderate contamination of river water by multiple contaminants could result in unfavourable living conditions and cause detectable stress for aquatic organisms.     

Effects of a major municipal effluent on the St. Lawrence River: A case study

The St. Lawrence River (SLR) is the second largest waterway in North America. The discharge of the City of Montreal wastewater treatment plant (WWTP) represents the largest volume of treated wastewaters being released into the river. It also ranks as the largest sewage treatment plant of its kind in North America. Over the last decade, intensive multidisciplinary research has focused on assessing the impacts of Montreal wastewater effluents on the SLR. We describe the major findings of these investigations, including the determination of the fate of contaminants, bioaccumulation in fish and invertebrates, ecotoxicological measurements of aquatic animal health, evaluation of endocrine disruption, parasitism in fish, and combined effects of multiple stressors on the SLR. Impacts of the effluents from the WWTP on aquatic organisms from the SLR are both toxicological and ecological, demonstrating the need for an integrated view of the impacts of municipal effluents on aquatic ecosystems.