Contributions of phosphatase and microbial activity to internal phosphorus loading and their relation to lake eutrophication

Phosphatase may accelerate the process of lake eutrophication through improving phosphorus bioavailability. This mechanism was studied in three Chinese eutrophic shallow lakes (Lake Taihu, Lake Longyang,and Lake Lianhua). Phosphatase activity was related to the concentration of soluble reactive phosphorus (SRP) and chlorophyll a. Stability of dissolved phosphatase in reverse micelles may be attributed to molecular size, conformation and active residues of the enzyme. At the site with Microcystis bloomed in Lake Taihu, dissolved phosphatase activity was higher and more stable in micelles, SRP concentrations were lower in interstitial water, the contents of different forms of phosphorus and the amounts of aerobic bacteria were lower while respiration efficiency was higher in sediments. Phosphobacteria, both inorganic and organic and other microorganisms were abundant in surface water but rare in sediments. Therefore, internal phosphorus may substantially flux into water column by enzymatic hydrolysis and anaerobic release, together with mobility of bacteria, thereby initiating the bloom. In short, biological mechanism may act in concert with physical and chemical factors to drive the internal phosphorus release and accelerate lake eutrophication.

Annual cycle of carbon, nitrogen and phosphorus in the Bohai Sea: A model study

The annual cycle of nutrient-phytoplankton dynamics in Bohai Sea (BS) is simulated using a coupled physical-biological model in this study. By comparison, the modeled seasonal variations of nutrients and primary productivity agree with observations rather well. Although the annual cycles of chlorophyll a and primary production are both characterized by a double-peak configuration, a structural difference is still apparent: the phytoplankton biomass reaches the highest value in spring while summer is characterized by the most productivity in the BS, which can be ascribed to the combined impact of seawater temperature and zooplankton-grazing pressure on the growth of algae. Based on the validated simulations, the annual budgets of carbon, nitrogen and phosphorus are estimated, and are about 0.82 mt C surplus, 39 kt N deficit and 12kt P surplus, respectively, implying that the BS ecosystem is somewhat nitrogen limited. The contribution of two external nutrient sources, namely river discharges and resuspended sediments, to the growth of algae is also examined numerically, and it is found that the influence of river-borne nutrients mainly concentrates in estuaries, whereas the reduction of sediment-borne nutrients may significantly inhibit the onset of algae bloom in the whole BS. (c) 2007 Elsevier Ltd. All rights reserved.

藻体对水环境中N、P及重金属Cu2+、Pb2+、Cd2+、Cr6+的吸附特征研究

随着全球生态环境的恶化，各国日益重视对水体中各种污染物的治理。利用藻类的吸收、富集和降解作用，可以去除污水中的营养物质、重金属离子和有机污染物，与其他物理、化学及工程的方法相比，该技术具有以下优点：成本低、能耗小、治理效果较好，对环境污染小，有利于资源化，有利于整体生态环境的改善，是治理水质污染的新途径。 本文利用几种大型海藻对富营养化海水进行处理，结果发现孔石莼、刚毛藻均有很强的吸收N、P的能力，吸收能力依次为褶曲刚毛藻>束生刚毛藻>孔石莼。水体中褶曲刚毛藻3 g/L含量，在3～5小时之内，可把中等以上富营养化海水中的N、P降低至一类海水水平。利用刚毛藻处理富营养化地下海水和养殖废水，进行海参和大菱鲆养殖试验，探索藻类净化水质和废水循环利用的新模式，使水体保持较低的营养盐状态，减轻养殖废水对环境的影响，实现了海水养殖业与环境的可持续发展。 刚毛藻在我国近海滩涂分布广泛，利用它来处理富营养化水体，并和水产养殖业相结合，既净化水体，使养殖废水能循环利用，满足水产养殖的需求，又改善水产业生态环境。同时，将回收藻体生产优质饲料、食品和药物等，实现藻类资源的高值利用。刚毛藻营养丰富，用其替代鼠尾藻作海参饲料，资源丰富，成本低，效果好，是一种值得加以开发利用的宝贵资源，具有广泛的应用前景。 生物吸附法是一种经济有效的移除废水中有害重金属离子的方法。由于藻类细胞壁中的多聚糖可提供吸附重金属的位点，廉价而蕴藏丰富的海藻对多种重金属表现出很强的吸附能力。所以本文通过分批实验，研究了非活体刚毛藻对水体中重金属Cu2+、Pb2+和Cd2+的吸附影响因子、吸附热力学、吸附动力学及吸附机理，得到了平衡等温线及动力学数据。吸附过程的最佳pH值为5.0，吸附量随温度的升高而增加，水体中常见的Na+、K+、Ca2+、Mg2+阳离子及Cl-、NO3-、SO42-、C2O42-等阴离子的存在对吸附的影响并不显著。EDTA存在时，吸附百分率大大降低。吸附等温线符合Langmuir和Freundlich方程。刚毛藻对重金属Cu2+、Pb2+和Cd2+的吸附容量很高，25℃时，对Cu2+、Pb2+和Cd2+的最大吸附容量分别为1.61 mmol/g、0.96 mmol/g和0.98 mmol/g，且吸附过程为吸热反应。刚毛藻对重金属Cu2+、Pb2+和Cd2+的吸附过程为化学吸附，在吸附过程中藻体表面的官能团可能与金属离子发生了螯合作用。吸附动力学过程符合pseudo-二级动力学模型，在初始的30min内，吸附速率很快，随后速率逐渐降低。解吸试验表明，用EDTA可以对重金属进行回收，刚毛藻可以循环利用。实验结果表明刚毛藻是一种高效、经济实用的生物吸附材料，可用来吸附回收水体中的重金属Cu2+、Pb2+和Cd2+等。 通过非活体刚毛藻对重金属Cr6+的吸附影响因子、吸附动力学、吸附机理的研究发现，刚毛藻对Cr6+具有很强的还原能力，对电镀废水中的Cr6+的还原去除提供了非常好的方法。吸附过程的最佳pH值为2～3，实际电镀废水通常在此pH范围，因此处理实际废水时，首先在原酸性条件下，对Cr6+进行还原去除，然后调废水pH至5.0，继续进行吸附，去除其他二价离子及被还原的三价Cr离子，实现了利用同一材料还原Cr6+为Cr3+，并将Cr3+和其他重金属离子同时去除。通过对机理的讨论，认为刚毛藻对Cr6+的生物吸附过程不是一个简单的“离子交换过程”，而是一个“吸附还原过程”。在海藻量足够的前提下，只要时间足够长，Cr6+可被彻底还原去除。 利用工业废弃物褐藻渣，对水体中重金属离子Cu2+、Pb2+、Cd2+及Cr6+的生物吸附特性分别进行了讨论，结果表明褐藻渣对重金属离子的吸附特性与刚毛藻一致，吸附等温线符合Langmuir和Freundlich方程，在25℃时，pH为5.0时，由Langmuir方程求出褐藻渣对Cu2+、Pb2+和Cd2+的最大吸附容量分别为4.20 mmol/g、3.13 mmol/g和2.97 mmol/g。褐藻渣对低、高浓度的重金属Cr6+都具有很强的吸附能力，且移除效果比较彻底。实际应用结果表明，褐藻渣是一种高效、经济实用的生物吸附材料，可用来吸附回收水体中的重金属离子，具有广泛的应用前景。

Transfer and transport of phosphorus and silica in the turbidity maximum zone of the Changjiang estuary

The concentration of suspended particulate matter (SPM), sedimentation flux, and various forms of phosphorus and silica in turbidity maximum zone (TMZ) in the Changjiang (Yangtze) estuary was studied. Based on the budget of P and Si, their mass balances in the TMZ were calculated. Results show that the variation in concentration of dissolved inorganic silicon (DISi) was mainly controlled by seawater dilution, while that of dissolved inorganic phosphor-us (DIP) was considerably affected by the buffering of suspended matter and sediment. Our experiments showed that the sedimentation fluxes of SPM and particulate inorganic phosphorus (PIP), total particulate phosphorus (TPP), particulate inorganic silicon (PISi), and biological silicon (BSi) in the TMZ were 238.4 g m(-2) d(-1) and 28.3, 43.1, 79.0, 63.0 mg m(-2) d(-1), respectively. In addition, a simple method to estimate the ratio of resuspension of sediment in the TMZ was established, with which the rate in surface and bottom waters of the TMZ accounted for 55.7 and 66.1% of the total SPM, respectively, indicating that the sediment resuspension in the TMZ influenced significantly the mass balances of P and Si. Particulate adsorbed P (60.8%) and 35.5% of total particulate P discharged from the river were filtered and then deposited in the TMZ. The input flux of PIP from the river mouth was 55.9% of that of DIP, being important as biologically available P, while that of PISi was only 3.5% of DISi, showing that particulate adsorbed Si was much less important than particulate adsorbed P. (c) 2008 Elsevier Ltd. All rights reserved.

Investigating the removal of some pharmaceutical compounds in hospital wastewater treatment plants operating in Saudi Arabia

The concentrations of 12 pharmaceutical compounds (atenolol, erythromycin, cyclophosphamide, paracetamol, bezafibrate, carbamazepine, ciprofloxacin, caffeine, clarithromycin, lidocaine, sulfamethoxazole and Nacetylsulfamethoxazol (NACS)) were investigated in the influents and effluents of two hospital wastewater treatment plants (HWWTPs) in Saudi Arabia. The majority of the target analytes were detected in the influent samples apart from bezafibrate, cyclophosphamide, and erythromycin. Caffeine and paracetamol were detected in the influent at particularly high concentrations up to 75 and 12 ug/L, respectively. High removal efficiencies of the pharmaceutical compounds were observed in both HWWTPs, with greater than 90 % removal on average. Paracetamol, sulfamethoxazole, NACS, ciprofloxacin, and caffeine were eliminated by between >95 and >99 % on average. Atenolol, carbamazepine, and clarithromycin were eliminated by >86 % on average. Of particular interest were the high removal efficiencies of carbamazepine and antibiotics that were achieved by the HWWTPs; these compounds have been reported to be relatively recalcitrant to biological treatment and are generally only partially removed. Elevated temperatures and high levels of sunlight were considered to be the main factors that enhanced the removal of these compounds.

Environmental and biological characteristics of lagoons on the southwest coast of Ireland

Coastal lagoons are defined as shallow coastal water bodies partially separated from the adjacent sea by a restrictive barrier. Coastal lagoons are protected under Annex I of the European Habitats Directive (92/43/EEC). Lagoons are also considered to be “transitional water bodies” and are therefore included in the “register of protected areas” under the Water Framework Directive (2000/60/EC). Consequently, EU member states are required to establish monitoring plans and to regularly report on lagoon condition and conservation status. Irish lagoons are considered relatively rare and unusual because of their North Atlantic, macrotidal location on high energy coastlines and have received little attention. This work aimed to assess the physicochemical and ecological status of three lagoons, Cuskinny, Farranamanagh and Toormore, on the southwest coast of Ireland. Baseline salinity, nutrient and biological conditions were determined in order to provide reference conditions to detect perturbations, and to inform future maintenance of ecosystem health. Accumulation of organic matter is an increasing pressure in coastal lagoon habitats worldwide, often compounding existing eutrophication problems. This research also aimed to investigate the in situ decomposition process in a lagoon habitat together with exploring the associated invertebrate assemblages. Re-classification of the lagoons, under the guidelines of the Venice system for the classifications of marine waters according to salinity, was completed by taking spatial and temporal changes in salinity regimes into consideration. Based on the results of this study, Cuskinny, Farranamanagh and Toormore lagoons are now classified as mesohaline (5 ppt – 18 ppt), oligohaline (0.5 ppt – 5 ppt) and polyhaline (18 ppt – 30 ppt), respectively. Varying vertical, longitudinal and transverse salinity patterns were observed in the three lagoons. Strong correlations between salinity and cumulative rainfall highlighted the important role of precipitation in controlling the lagoon environment. Maximum effect of precipitation on the salinity of the lagoon was observed between four and fourteen days later depending on catchment area geology, indicating the uniqueness of each lagoon system. Seasonal nutrient patterns were evident in the lagoons. Nutrient concentrations were found to be reflective of the catchment area and the magnitude of the freshwater inflow. Assessment based on the Redfield molar ratio indicated a trend towards phosphorus, rather than nitrogen, limitation in Irish lagoons. Investigation of the decomposition process in Cuskinny Lagoon revealed that greatest biomass loss occurred in the winter season. Lowest biomass loss occurred in spring, possibly due to the high density of invertebrates feeding on the thick microbial layer rather than the decomposing litter. It has been reported that the decomposition of plant biomass is highest in the preferential distribution area of the plant species; however, no similar trend was observed in this study with the most active zones of decomposition varying spatially throughout the seasons. Macroinvertebrate analysis revealed low species diversity but high abundance, indicating the dominance of a small number of species. Invertebrate assemblages within the lagoon varied significantly from communities in the adjacent freshwater or marine environments. Although carried out in coastal lagoons on the southwest coast of Ireland, it is envisaged that the overall findings of this study have relevance throughout the entire island of Ireland and possibly to many North Atlantic coastal lagoon ecosystems elsewhere.

Impacts of Mountaintop Removal Coal Mining on the Mud River, West Virginia: Selenium Accumulation, Trophic Transfer, and Toxicity in Fish

Selenium (Se) is a micronutrient necessary for the function of a variety of important enzymes; Se also exhibits a narrow range in concentrations between essentiality and toxicity. Oviparous vertebrates such as birds and fish are especially sensitive to Se toxicity, which causes reproductive impairment and defects in embryo development. Selenium occurs naturally in the Earth's crust, but it can be mobilized by a variety of anthropogenic activities, including agricultural practices, coal burning, and mining.

Mountaintop removal/valley fill (MTR/VF) coal mining is a form of surface mining found throughout central Appalachia in the United States that involves blasting off the tops of mountains to access underlying coal seams. Spoil rock from the mountain is placed into adjacent valleys, forming valley fills, which bury stream headwaters and negatively impact surface water quality. This research focused on the biological impacts of Se leached from MTR/VF coal mining operations located around the Mud River, West Virginia.

In order to assess the status of Se in a lotic (flowing) system such as the Mud River, surface water, insects, and fish samples including creek chub (Semotilus atromaculatus) and green sunfish (Lepomis cyanellus) were collected from a mining impacted site as well as from a reference site not impacted by mining. Analysis of samples from the mined site showed increased conductivity and Se in the surface waters compared to the reference site in addition to increased concentrations of Se in insects and fish. Histological analysis of mined site fish gills showed a lack of normal parasites, suggesting parasite populations may be disrupted due to poor water quality. X-ray absorption near edge spectroscopy techniques were used to determine the speciation of Se in insect and creek chub samples. Insects contained approximately 40-50% inorganic Se (selenate and selenite) and 50-60% organic Se (Se-methionine and Se-cystine) while fish tissues contained lower proportions of inorganic Se than insects, instead having higher proportions of organic Se in the forms of methyl-Se-cysteine, Se-cystine, and Se-methionine.

Otoliths, calcified inner ear structures, were also collected from Mud River creek chubs and green sunfish and analyzed for Se content using laser ablation inductively couple mass spectrometry (LA-ICP-MS). Significant differences were found between the two species of fish, based on the concentrations of otolith Se. Green sunfish otoliths from all sites contained background or low concentrations of otolith Se (< 1 µg/g) that were not significantly different between mined and unmined sites. In contrast creek chub otoliths from the historically mined site contained much higher (≥ 5 µg/g, up to approximately 68 µg/g) concentrations of Se than for the same species in the unmined site or for the green sunfish. Otolith Se concentrations were related to muscle Se concentrations for creek chubs (R2 = 0.54, p = 0.0002 for the last 20% of the otolith Se versus muscle Se) while no relationship was observed for green sunfish.

Additional experiments using biofilms grown in the Mud River showed increased Se in mined site biofilms compared to the reference site. When we fed fathead minnows (Pimephales promelas) on these biofilms in the laboratory they accumulated higher concentrations of Se in liver and ovary tissues compared to fathead minnows fed on reference site biofilms. No differences in Se accumulation were found in muscle from either treatment group. Biofilms were also centrifuged and separated into filamentous green algae and the remaining diatom fraction. The majority of Se was found in the diatom fraction with only about 1/3rd of total biofilm Se concentration present in the filamentous green algae fraction

Finally, zebrafish (Danio rerio) embryos were exposed to aqueous Se in the form of selenate, selenite, and L-selenomethionine in an attempt to determine if oxidative stress plays a role in selenium embryo toxicity. Selenate and selenite exposure did not induce embryo deformities (lordosis and craniofacial malformation). L-selenomethionine, however, induced significantly higher deformity rates at 100 µg/L compared to controls. Antioxidant rescue of L-selenomethionime induced deformities was attempted in embryos using N-acetylcysteine (NAC). Pretreatment with NAC significantly reduced deformities in the zebrafish embryos secondarily treated with L-selenomethionine, suggesting that oxidative stress may play a role in Se toxicity. Selenite exposure also induced a 6.6-fold increase in glutathione-S-transferase pi class 2 gene expression, which is involved in xenobiotic transformation. No changes in gene expression were observed for selenate or L-selenomethionine-exposed embryos.

The findings in this dissertation contribute to the understanding of how Se bioaccumulates in a lotic system and is transferred through a simulated foodweb in addition to further exploring oxidative stress as a potential mechanism for Se-induced embryo toxicity. Future studies should continue to pursue the role of oxidative stress and other mechanisms in Se toxicity and the biotransformation of Se in aquatic ecosystems.