Oxygen,carbon, and nutrient exchanges at the sediment–water interface in the Mar Piccolo of Taranto (Ionian Sea,southern Italy)

In the shallow environment, the nutrient and carbon exchanges at the sediment–water interface contribute significantly to determine the trophic status of the whole water column. The intensity of the allochthonous input in a coastal environment subjected to strong anthropogenic pressures determines an increase in the benthic oxygen demand leading to depressed oxygen levels in the bottom waters. Anoxic conditions resulting from organic enrichment can enhance the exchange of nutrients between sediments and the overlying water. In the present study, carbon and nutrient fluxes at the sediment–water interface were measured at two experimental sites, one highly and one moderately contaminated, as reference point. In situ benthic flux measurements of dissolved species (O₂, DIC, DOC, N-NO₃ ^?, N-NO₂ ^?, N-NH₄ ⁺, P-PO₄ ^3?, Si-Si(OH)₄, H₂S) were conducted using benthic chambers. Furthermore, undisturbed sediment cores were collected for analyses of total and organic C, total N, and biopolymeric carbon (carbohydrates, proteins, and lipids) as well as of dissolved species in porewaters and supernatant in order to calculate the diffusive fluxes. The sediments were characterized by suboxic to anoxic conditions with redox values more negative in the highly contaminated site, which was also characterized by higher biopolymeric carbon content (most of all lipids), lower C/N ratios and generally higher diffusive fluxes, which could result in a higher release of contaminants. A great difference was observed between diffusive and in situ benthic fluxes suggesting the enhancing of fluxes by bioturbation and the occurrence of biogeochemically important processes at the sediment–water interface. The multi-contamination of both inorganic and organic pollutants, in the sediments of the Mar Piccolo of Taranto (declared SIN in 1998), potentially transferable to the water column and to the aquatic trophic chain, is of serious concern for its ecological relevance, also considering the widespread fishing and mussel farming activities in the area.     

Spatiotemporal distribution of water environmental capacity—a case study on the western areas of Taihu Lake in Jiangsu Province,China

Currently, the poor water quality in Taihu Lake is a major problem in China, so pollution control in the upstream areas has become a government priority. In Jiangsu Province, pollution emissions around the western areas of Taihu Lake, including Changzhou Municipality and Yixing City, need to be highly restricted, and calculating the water environmental capacity is important if pollution is to be reduced. In this study, 19 control units in these areas were established, and a 0-D mathematical model was used to calculate the water environmental capacity. For three important control units with important cross sections, a 1-D model was established to redress the results. Finally, the total maximum monthly loads of each control unit were obtained using temporal allocation principles. The results suggested that (1) the total pollution control of chemical oxygen demand was 58,894.2 tonnes per annum (t a^?1), with ammonia nitrogen, total nitrogen, and total phosphorus amounting to 3,808, 6,054.6, and 386.6 t a^?1, respectively; (2) water environmental capacity per unit water area in the ambient control units was smaller than that in the middle control units; and (3) the largest water environmental capacity was in June, and the smallest capacity was in December. The study provides important information for local governments, which will enable them to implement pollution control strategies that will improve the water quality in Taihu Lake.     

Phosphorus fluxes at the sediment–water interface in subtropical wetlands subjected to experimental warming: A microcosm study

Global warming is increasingly challenging for wetland ecological function. A temperature controlled microcosm system was developed to simulate climate change scenarios of an ambient temperature (control) and an elevated temperature (+5 °C). The effects and associated mechanisms of warming on phosphorus (P) fluxes at the sediment–water interface of six subtropical wetlands were investigated. The results indicated that P fluxes were generally enhanced under the experimental warming as measured by higher P concentrations in the porewater and overlying water as well as higher benthic P fluxes. The release of P from sediment to porewater occurred more strongly and quickly in response to experimental warming compared to the subsequent upward transfer into overlying water. The average accumulative benthic P output from the tested wetlands under the experimental warming was greater by 12.9 μg cm^?2 y^?1 (28%) for total P and 8.26 μg cm^?2 y^?1 (25%) for dissolved reactive P, compared to the ambient scenarios. Under warming the redistribution of P fractions in sediments occurred with greater NH₄Cl–P and lower BD–P (extracted by a bicarbonate buffered dithionite solution) accompanied by greater NaOH–P. The higher temperature enhanced total phospholipid fatty acids. A shift in the microbial community was also observed with a relative dominance of fungi (a 4.7% increase) and a relative decline (by 18%) in bacterial abundance, leading to the higher secretion of phosphatase. Comparing between wetlands, the potential P fluxes in the nutrient-enriched wetlands were less impacted by warming than the other wetland types investigated. Thus wetlands characterized by low or medium concentrations of P in sediments were more susceptible to warming compared to P-rich wetlands.     

Degradation of rizazole in water–sediment systems

This study investigated the degradation of rizazole in water-sediment systems (West Lake system, WL; Beijing–Hangzhou Grand Canal system, BG) with two different types of sediments under aerobic and anaerobic conditions. The half-lives of rizazole in the WL water phase (14.59–15.13 d) were similar to those in the BG water phase (15.90–16.46 d). Within 3–7 d, the rizazole concentration in the sediments reached the maximum values, i.e., equilibrium. Rizazole dissipation was faster in the WL sediment phase with higher organic matter content (T_1/2 = 18.99–19.09 d) compared with the BG sediment phase (T_1/2 = 31.08–33.32 d). Rizazole degradation was slightly faster in the West Lake water-sediment system (WL system) (T_1/2 = 17.11–18.05 d) than in the Beijing–Hangzhou Grand Canal water—sediment system (BG system) (T_1/2 = 20.51–25.02 d). The aerobic degradation of rizazole was similar to its anaerobic degradation in the water-sediment system. The findings are useful to understand the behavior of pesticide in environment.     

Metabolic fate of the 14C-labeled herbicide clodinafop-propargyl in a sediment–water system

The metabolic fate of ¹⁴C-phenyl-labeled herbicide clodinafop-propargyl (¹⁴C-CfP) was studied for 28 days in lab assays using a sediment–water system derived from a German location. Mineralization was 5.21% of applied ¹⁴C after 28 days exhibiting a distinct lag phase until day 14 of incubation. Portions of radioactivity remaining in water phases decreased at moderate rate to 18.48% after 28 days; 62.46% were still detected in water after 14 days. Soxhlet extraction of the sediment using acetonitrile released 35.56% of applied ¹⁴C with day 28, while 33.99% remained as non-extractable residues. A remarkable increase of bound ¹⁴C was observed between 14 and 28 days correlating with the distinct increase of mineralization. No correlation was found throughout incubation with microbial activity of the sediment as determined by dimethyl sulfoxide reduction. Dissolved oxygen and pH value of water phases remained almost constant for 28 days. Analyses of Soxhlet extracts of the sediment and ethyl acetate extracts of water phases by radio-TLC and radio-HPLC revealed that CfP was rapidly cleaved to free acid clodinafop (Cf), which was further (bio-) transformed. DT₅₀ values (based on radio-HPLC) were below 1 day (CfP) and slightly above 28 days (Cf). Further metabolites were not detected. Fractionation of humic and non-humic components of the sediment demonstrated that CfP's non-extractable residues were predominantly associated with fulvic acids up to 14 days of incubation (3.36%), whereas after 28 days, the majority of radioactivity was found in the humin/mineral fraction (13.30% of applied ¹⁴C). Due to high-performance size-exclusion chromatography of the fulvic acids fraction derived from assays incubated for 28 days, this portion of ¹⁴C was firmly, possibly covalently bound to fulvic acids and did not consist of CfP or Cf. Using an isolation strategy comprising preincubation of sediment with CfP and mineralization of ¹⁴C-CfP as criterion, a microorganism was isolated from the sediment examined. It grew on ¹⁴C-CfP as sole carbon source with evolution of ¹⁴CO₂. The bacterium was characterized by growth on commonly used carbon sources and 16S rDNA sequence analysis. Its sequence exhibited high similarity with that of Nocardioides aromaticivorans strain H-1 (98.85%; DSM 15131, JCM 11674).     

Concentrations of some heavy metals in water, sediment and fish species from the Atatürk Dam Lake (Euphrates), Turkey

Concentrations of heavy metals (Cd, Co, Cu, Fe, Hg, Mn, Mo, Ni, Pb and Zn) were measured in the water, sediment and fish species (Acanthobrama marmid, Chalcalburnus mossulensis, Chondrostoma regium, Carasobarbus luteus, Capoetta trutta and Cyprinus carpio) from the Atatürk Dam Lake, Turkey. Among the heavy metals studied Cd, Co, Hg, Mo and Pb were not detected in water, sediments and fish samples, while Ni was undetectable levels in fish samples. Levels of Cu, Fe, Mn and Zn varied depending on different tissues. The results of this study indicated that a general absence of serious pollution in the dam lake is due to heavy metals, where as the concentrations of elements found could mainly be attributed to geological sources.     

Hexadecane and pristane degradation potential at the level of the aquifer—evidence from sediment incubations compared to in situ microcosms

Monitored natural attenuation is widely accepted as a sustainable remediation method. However, methods providing proof of proceeding natural attenuation within the water-unsaturated (vadose) zone are still relying on proxies such as measurements of reactive and non-reactive gases, or sediment sampling and subsequent mineralisation assays, under artificial conditions in the laboratory. In particular, at field sites contaminated with hydrophobic compounds, e.g. crude oil spills, an in situ evaluation of natural attenuation is needed, because in situ methods are assumed to provide less bias than investigations applying either proxies for biodegradation or off-site microcosm experiments. In order to compare the current toolbox of methods with the recently developed in situ microcosms, incubations with direct push-sampled sediments from the vadose and the aquifer zones of a site contaminated with crude oil were carried out in conventional microcosms and in situ microcosms. The results demonstrate the applicability of the in situ microcosm approach also outside water-saturated aquifer conditions in the vadose zone. The sediment incubation experiments demonstrated turnover rates in a similar range (vadose, 4.7 mg/kg*day; aquifer, 6.4 mg_hexadecane/kg_soil/day) of hexadecane degradation in the vadose zone and the aquifer, although mediated by slightly different microbial communities according to the analysis of fatty acid patterns and amounts. Additional experiments had the task of evaluating the degradation potential for the branched-chain alkane pristane (2,6,10,14-tetramethylpentadecane). Although this compound is regarded to be hardly degradable in comparison to n-alkanes and is thus frequently used as a reference parameter for indexing the extent of biodegradation of crude oils, it could be shown to be degraded by means of the incubation experiments. Thus, the site had a high inherent potential for natural attenuation of crude oils both in the vadose zone and the aquifer.     

Concentrations of heavy metal and radioactivity in surface water and sediment of Hazar Lake (Elaziğ, Turkey)

Concentration of heavy metals and natural gross radioactivity were measured in the surface water and sediment of Hazar Lake (Elazi?, Turkey). Eight sampling sites were pre-defined in different locations of the lake. A preliminary study on heavy metals (Zn, Fe, Mn, Ni, Cu, Cr, Co and Pb), major elements (Na, K, Ca, Mg) concentrations and natural radioactivity related to 226Ra, gross-alpha and gross-beta radiations in the surface water and deep sediments were determined. The obtained results showed that, in general, the heavy metals (Zn, Fe, Mn, Ni, Cu and Pb) and major elements (Na, K, Ca, Mg) concentrations in water did not exceed WHO (World Health Organization, 1999), EC (Europe Community, 1998), EPA (Environment Protection Agency, 2002) and TSE-266 (Turkish Standard, 1997) guidelines. Generally, heavy metals and major elements concentration of the sediments were found decrease in sequence of Fe>Mg>Ca>Mn>Zn>Ni>Cr>Cu>Co>Pb. The results of this study indicated that a general absence of serious pollution in the Hazar Lake. The results obtained from the radioactivity determination indicate that the surface water radioactivity concentration of 226Ra, gross-alpha and gross-beta were ranging from 0.52+/-0.02 to 2.02+/-0.06 Bq/l and from 0.65+/-0.03 to 2.52+/-0.07 Bq/l and from 0.01+/-0.01 to 0.14+/-0.01 Bq/l, respectively. Deep sediment radioactivity concentrations of 226Ra is ranging from 0.07+/-0.03 to 0.32+/-0.07 Bq/g.     

Evidence of the water-cage effect on the photolysis of NO3− and FeOH2+. Implications of this effect and of H2O2 surface accumulation on photochemistry at the air–water interface of atmospheric droplets

Experiments are conducted to determine the effect of a cage of water molecules on the photolysis quantum yields of nitrate, FeOH²⁺, and H₂O₂. Results suggest that the quantum yields of nitrate and FeOH²⁺ are decreased by the recombination of photo-fragments ( OH +  NO₂ and Fe²⁺ +  OH, respectively) before they leave the surrounding cage of water molecules. However, no evidence is found for an enhanced quantum yield for H₂O₂. Therefore, the photolysis of nitrate and FeOH²⁺ could be enhanced if the cage of the solvent molecules is incomplete, as is the case at the air–water interface of atmospheric droplets. The photolysis rate constant distribution within nitrate, FeOH²⁺, and H₂O₂ aerosols is calculated by combining the expected quantum yield data in the bulk and at the interface with Mie theory calculations of light intensity. The photolysis rate constant of nitrate and FeOH²⁺ would be significantly higher at the surface than in the bulk if quantum yields are enhanced at the surface. In the case of H₂O₂, the photolysis rate constant would be enhanced by surface accumulation. The results concerning the expected rates of photolysis of these photoactive species are applied to the assessment of the reaction between benzene and OH in the presence of OH scavengers in an atmospherically relevant scenario. For a droplet of 1 μm radius, a large fraction of the total OH-benzene reaction (15% for H₂O₂, 20% for nitrate, and 35% for FeOH²⁺) would occur in the surface layer, which accounts for just 0.15% of the droplet volume.     

Determination of cyclic volatile methylsiloxanes in water,sediment, soil,biota, and biosolid using large-volume injection–gas chromatography–mass spectrometry

Several methods were developed to detect the cyclic volatile methylsiloxanes (cVMSs) including octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in water, sediment, soil, biota, and biosolid samples. Analytical techniques employed to optimize measurement of this compound class in various matrices included membrane-assisted solvent extraction in water, liquid–solid extraction for sediment, soil, biota, and biosolid samples. A subsequent analysis of the extract was conducted by large-volume injection–gas chromatography−mass spectrometry (LVI−GC−MS). These methods employed no evaporative techniques to avoid potential losses and contamination of the volatile siloxanes. To compensate for the inability to improve detection limits by concentrating final sample extract volumes we used a LVI–GC–MS. Contamination during analysis was minimized by using a septumless GC configuration to avoid cVMS’s associated with septum bleed. These methods performed well achieving good linearity, low limits of detection, good precision, recovery, and a wide dynamic range. In addition, stability of cVMS in water and sediment was assessed under various storage conditions. D4 and D5 in Type-I (Milli-Q) water stored at 4 °C were stable within 29 d; however, significant depletion of D6 (60–70%) occurred only after 3 d. Whereas cVMS in sewage influent and effluent were stable at 4 °C within 21 d. cVMS in sediment sealed in amber glass jars at −20 °C and in pentane extracts in vials at −15 °C were stable during 1 month under both storage conditions.     

Study on the threshold relationship between landscape pattern and water quality considering spatial scale effect—a case study of Dianchi Lake Basin in China

Environmental Science and Pollution Research - It is of great significance to analyze the threshold relationship between landscape pattern and water quality for watershed water environment...     

Effect of short-chain organic acids and pH on the behaviors of pyrene in soil–water system

The effects of five short-chain organic acids (SCOAs) on the behaviors of pyrene in soil–water system were investigated. The influences of the quantity and species of organic acids, pH, and soil dissolved organic matter were considered. The results showed the presence of SCOAs inhibited the adsorption and promoted the desorption of pyrene in the following order: citric acid > oxalic acid > tartaric acid > lactic acid > acetic acid. The decreased extents of pyrene adsorption performance enhanced with increasing SCOA concentrations, while the decreasing rate became less pronounced at high SCOA concentrations. In the presence of organic acids, the adsorption ability of pyrene decreased with increasing pH. However, there was a slight increase of pyrene adsorption with the addition of oxalic acid, tartaric acid and citric acid above pH 8. The capacity for pyrene retention differentiated significantly between the soils with and without dissolved organic matter. The presence of SCOAs was also favorable for the decrease of pyrene adsorption on soil without dissolved organic matter. The results of this study have important implications for the remediation of persistent organic pollutants in soil and groundwater.     

Thermal degradation of hexachlorobenzene in the presence of calcium oxide at 340–400 °C

Hexachlorobenzene (HCB) in the milligram range was co-heated with calcium oxide (CaO) powder in sealed glass ampoules at 340–400 °C. The heated samples were characterized and analyzed by Raman spectroscopy, elemental analysis, gas chromatography/mass spectrometry, ion chromatography, and thermal/optical carbon analysis. The degradation products of HCB were studied at different temperatures and heated times. The amorphous carbon was firstly quantitatively evaluated and was thought to be important fate of the C element of HCB. The yield of amorphous carbon in products increased with heating time, for samples treated for 8 h at 340, 380 °C and 400 °C, the value were 17.5%, 34.8% and 50.2%, respectively. After identification of the dechlorination products, the HCB degradation on CaO at 340–400 °C was supposed to through dechlorination/polymerization pathway, which is induced by electron transfer, generate chloride ions and form high-molecular weight intermediates with significant levels of both hydrogen and chlorine, and finally form amorphous carbon. Higher temperature was beneficial for the dechlorination/polymerization efficiency. The results are helpful for clarifying the reaction mechanism for thermal degradation of chlorinated aromatics in alkaline matrices.     

Spatial Trends of Trace-Element Contamination in Recently Deposited Lake Sediment Around the Ni–Cu Smelter at Nikel, Kola Peninsula, Russian Arctic

A large copper–nickel smelter complex is located at the Kole Penninsula, Russia, close to the Norwegian border. Trace-element concentrations in surface sediments (0–0.5 cm) and pre-industrial sediments from 45 lakes in the region were used to uncover spatial deposition patterns and contamination factor of sediments. Elevated concentrations were found, especially for Ni and Cu, but also for Pb, Co, Hg, As, and Cd. Highest concentrations were found up to 20 km from the smelter, but the concentrations decreased exponentially with distance from the smelter. Increasing Ni, Cu, As, and Hg concentrations from sub-surface to surface sediments were found for lakes at intermediate distances (20–60 km). This may reflect recent changes in atmospheric depositions, as shown in nearby Norwegian areas. However, we cannot rule out that this also may have been caused by diagenetic processes, especially for the most redox-sensitive elements such as As.     

Optimal water and land resource allocation in pastoral areas based on a water–land forage–livestock balance: a case study of Otog Front Banner,Inner Mongolia,China

Environmental Science and Pollution Research - Natural grasslands provide important land resources in pastoral areas, and greatly contribute to ecological functioning. Overgrazing and other...     

An observational study of the HONO–NO2 coupling at an urban site in Guangzhou City,South China

The temporal behavior of HONO and NO₂ was investigated at an urban site in Guangzhou city, China, by means of a DOAS system during the Pearl River Delta 2006 intensive campaign from 10 to 24 July 2006. Within the whole measurement period, unexpected high HONO mixing ratios up to 2 ppb were observed even during the day. A nocturnal maximum concentration of about 8.43 ± 0.4 ppb was detected on the night of 24 July 2006. Combining the data simultaneously observed by different instruments, the coupling of HONO–NO₂ and the possible formation sources of HONO are discussed. During the measurement period, concentration ratios of HONO to NO₂ ranged from (0.03 ± 0.1) to (0.37 ± 0.09), which is significantly higher than previously reported values (0.01–0.1). Surprisingly, in most cases a strong daytime correlation between HONO and NO₂ was found, contrary to previous observations in China. Aerosol was found to have a minor impact on HONO formation during the whole measurement period. Using a pseudo steady state approach for interpreting the nocturnal conversion of NO₂ to HONO suggests a non-negligible role of the relative humidity for the heterogeneous HONO formation from NO₂.     

Air–water exchange fluxes of polycyclic aromatic hydrocarbons in the tropical coast,Taiwan

Air–water exchange fluxes of polycyclic aromatic hydrocarbons (PAHs) were simultaneously measured in air and water samples from two sites on the Kenting coast, located at the southern tip of Taiwan, from January to December 2010. There was no significant difference in the total PAH (t-PAH) concentrations in both gas and dissolved phases between these two sites due to the less local input which also coincided to the low levels of t-PAH concentration; the gas and dissolved phases averaged 1.29 ± 0.59 ng m^?3 and 2.17 ± 1.19 ng L^?1 respectively. The direction and magnitude of the daily flux of PAHs were significantly influenced by wind speed and dissolved PAH concentrations. Individual PAH flux ranged from 627 ng m^?2 d^?1 volatilization of phenanthrene during the rainy season with storm–water discharges raising dissolved phase concentration, to 67 ng m^?2 d^?1 absorption of fluoranthene during high wind speed periods. Due to PAH annual fluxes through air–water exchange, Kenting seawater is a source of low molecular weight PAHs and a reservoir of high molecular weight PAHs. Estimated annual volatilization fluxes ranged from 7.3 μg m^?2 yr^?1 for pyrene to 50 μg m^?2 yr^?1 for phenanthrene and the absorption fluxes ranged from ?2.6 μg m^?2 yr^?1 for chrysene to ?3.5 μg m^?2 yr^?1 for fluoranthene.     

Influence of the presence of ruthenium on the activity and stability of Co–Mg–Al-based catalysts in CO2 reforming of methane for syngas production

Environmental Science and Pollution Research - Hydrogen production by methane dry reforming is an important yet challenging process. A performing catalyst will favor the thermodynamic equilibrium...     

Mercury in sediment and fish communities of Lake Vänern, Sweden: recovery from contamination

The past effluents of mercury (Hg) into Lake V?nern were considerable. The consequences of, and recovery from these have been monitored through continuous measurements of mercury in sediment and fish. Mercury levels in lake sediments in the vicinity of the main source of mercury, a chloralkali plant on the northern shore, have only decreased by slightly more than a half since the mid-1970s, despite a radical decrease in effluents from the source, already during the 1960s. The mercury levels in pike (Esox lucius) have decreased to a similar extent during this time period. They are now about 30% higher in the worst affected parts of the lake compared to the least affected parts. Lower levels have been measured in perch (Perca fluviatilis) and salmonoid fish in the lake. Despite the increased presence of mercury in the sediment of Lake V?nern, the mercury levels in the fish of the lake are relatively low compared to fish in lakes situated in the same region, but not affected by any local mercury effluents. As calculated, the total fish biomass of L. V?nern holds less than 1000th of the amount of mercury contained in the upper, biologically active layers of the bottom sediment of the lake. This demonstrates the potential influence of various environmental factors and motivates continued monitoring of mercury levels in the lake in the future.     

Influence of hydroxypropyl-β-cyclodextrin on the biodegradation of C-phenanthrene and C-hexadecane in soil

Soil was spiked with [9-¹⁴C]phenanthrene and [1-¹⁴C]hexadecane at 50 mg kg⁻¹ and aged for 1, 25, 50, 100 and 250 d. At each time point, the microcosms were amended with aqueous solutions of cyclodextrin (HP-β-CD) at a range of concentrations (0-40 mM). Mineralisation assays and aqueous HP-β-CD extractions were performed to assess the effect of the amendments on microbial degradation. The results showed that amendments had no significant impact on the microbial degradation of either of the ¹⁴C-contaminants. Further, HP-β-CD extractions were correlated with the mineralisation of the target chemicals in each of the soil conditions. It was found that the HP-β-CD extraction was able to predict mineralisation in soils which had not been amended with cyclodextrin; however, in the soils containing the HP-β-CD, there was no predictive relationship. Under the conditions of this study, the introduction of HP-β-CD into soils did not enhance the biodegradation of the organic contaminants.