Behavior and stability of organic contaminant droplets in aqueous solutions

The behavior of several hydrophobic organic compounds (HOCs) in water at concentrations close to and above their maximum solubility values was studied. For this purpose, solutions of benzene, toluene, xylene, trichloroethylene (TCE) and a mixture of them were prepared in excess in freshwater and in saltwater, and solution stability was examined. High organic concentrations were found to remain stable in both freshwater and saltwater. In saltwater, for example, toluene and xylene concentrations remained as high as 14 and 26 times their solubilities, respectively, over a period of 6 days, while in freshwater, their concentrations remained 8 and 30 times their solubilities over the same period. This phenomenon is attributed to the presence of stable organic droplets, which were observed using optical microscopy. In addition, the transport of HOC droplets through sand is demonstrated, using an experimental system consisting of a saltwater source reservoir connected by a porous inactive sand layer to a freshwater collector reservoir.     

Applicability of a sharp-interface model for estimating steady-state salinity at pumping wells--validation against sand tank experiments

A numerical sharp-interface model of saltwater and freshwater behavior was validated against experiments conducted in two small scale sand tanks. A simple algorithm was proposed to determine saltwater and freshwater withdrawal rates at a pumping well at which a total pumping rate was specified. Model estimates were compared with transient salinity breakthroughs and steady-state salinities of water extracted from pumping wells in the sand tanks. Experimental scenarios included various combinations of freshwater pumping and injection and saltwater pumping. The corresponding Nash-Sutcliffe model efficiency was 0.95, which showed that the agreement between observations and computed results was satisfactory.     

Chronic toxicity of tributyltin to development and reproduction of the European freshwater snail Lymnaea stagnalis (L.)

Chronic toxicity, growth and reproduction were measured in the freshwater gastropod Lymnaea stagnalis exposed to waterborne bis(tri-n-butyltin) oxide (TBTO) over a range of four nominal concentrations (0-10microg TBTl(-1)). Egg development was completely inhibited at 10microg TBTl(-1), whilst abnormal embryonic development was observed at 1microg TBTl(-1). For the solvent control and the 0.01microg TBTl(-1)treatment group, normal development of L. stagnalis was observed. Survivorship of hatchlings was significantly reduced by TBT at 1microgl(-1) while inhibition of shell growth of L. stagnalis was also observed at this concentration. The data were used to determine intrinsic growth rates (r) using two theoretical approaches (the Euler-Lotka equation and a Leslie Matrix). Both approaches showed that survival, fecundity and population growth rate were reduced at 1microg TBTl(-1). Interestingly, at 0.01microg TBTl(-1) snails showed a higher fecundity and growth rate than in the solvent control. The TBT concentration at which the r would equal zero (ECr(0)) and the population NOEC (No Observed Effect Concentration) were estimated. The population NOEC was defined as either the lower 95% confidence or lower 95% pointwise percentile limit of the ECr(0). Values obtained using the two different approaches were similar and thus a geometric mean was calculated to obtain a final representative population NOEC value for L. stagnalis of 2745ng TBTl(-1). The present data together with chronic toxicity TBT data for freshwater organisms, obtained from peer-reviewed literature, were used to construct a species sensitivity distribution (SSD). A predicted no effect concentration was then derived from the SSD (hazardous concentration at 5%, i.e., HC5 or 95% protection level). This SSD was compared with the SSD derived from saltwater species datasets. The HC5 value for saltwater species (3.55ng TBTl(-1); lower confidence limit: 1.93ng TBTl(-1)) was significantly lower than that for freshwater species (30.13ng TBTl(-1); lower confidence limit: 9.23ng TBTl(-1)), indicating that saltwater species are probably more susceptible to TBT than their freshwater counterparts.     

Trifluoroacetic acid in ancient freshwater

Substantial concentrations (typically 10–100 ng/l) of trifluoroacetic acid (TFA) have been reported in contemporary saltwater and freshwater. It is well established that TFA is produced as the result of industrial activities. It is unclear whether there are any significant natural sources of this compound. To provide insight into the likely magnitude of possible natural sources of TFA we collected five samples of pre-industrial (>2000 year old) freshwater from Greenland and Denmark; there was no detectable TFA (<2 ng/l) in any of these samples. The available data suggest that TFA is not a naturally occurring trace component of the freshwater environment.     

Fate and transport of monoterpenes through soils. Part II: calculation of the effect of soil temperature, water saturation and organic carbon content

This theoretical study was performed to investigate the influence of soil temperature, soil water content and soil organic carbon fraction on the mobility of monoterpenes (C10HnOn') applied as pesticides to a top soil layer. This mobility was expressed as the amount volatilized and leached from the contaminated soil layer after a certain amount of time. For this, (slightly modified) published analytical solutions to a one dimensional, homogeneous medium, diffusion/advection/biodegradation mass balance equation were used. The required input-parameters were determined in a preceding study. Because the monoterpenes studied differ widely in the values for their physico-chemical properties, the relative importance of the various determinants also differed widely. Increasing soil water saturation reduced monoterpene vaporization and leaching losses although a modest increase was usually observed at high soil water contents. Organic matter served as the major retention domain, reducing volatilization and leaching losses. Increasing temperature resulted in higher volatilization and leaching losses. Monoterpene mobility was influenced by vertical water flow. Volatilization losses could be reduced by adding a clean soil layer on top of the contaminated soil. Detailed insight into the specific behaviour of different monoterpenes was obtained by discussing intermediate calculation results; the transport retardation factors and effective soil diffusion coefficients. One insight was that the air-water interface compartment is probably not an important partitioning domain for monoterpenes in most circumstances. The results further indicated that biodegradation is an important process for monoterpenes in soil.     

Influence of seaward boundary condition on contaminant transport in unconfined coastal aquifers.

Contaminant transport in coastal aquifers is complicated partly due to the conditions at the seaward boundary including seawater intrusion and tidal variations of sea level. Their inclusion in modelling this system will be computationally expensive. Therefore, it will be instructive to investigate the consequence of simplifying the seaward boundary condition by neglecting the seawater density and tidal variations in numerical predictions of contaminant transport in this zone. This paper presents a comparison of numerical predictions for a simplified seaward boundary condition with experimental results for a corresponding realistic one including a saltwater interface and tidal variations. Different densities for contaminants are considered. The comparison suggests that the neglect of the seawater intrusion and tidal variations does not affect noticeably the overall migration rate of the plume before it reaches the saltwater interface. However, numerical prediction shows that a more dense contaminant travels further seaward and part of the solute mass exits under the sea if the seawater density is not included. This is not consistent with the experimental result, which shows that the contaminant travels upwards to the shoreline along the saltwater interface. Neglect of seawater density, therefore, will result in an underestimation of the exit rate of solute mass around the coastline and fictitious migration paths under the seabed. For a less dense contaminant, neglect of seawater density has little effect on numerical prediction of migration paths.     

Boundary layer photochemistry simulated with a two-stream convection scheme

We explore the sensitivity of the simulation of photochemical smog to the turbulent mixing scheme, using two diffusion schemes and an original two-stream model (TSM) scheme, assuming in the column an updraft and a downdraft. In this latter scheme both updraft and downdraft concentrations are prognostic variables, unlike in previously proposed schemes. The comparisons are made using a one-dimensional column model, in a Eulerian or a Lagrangian mode. The diffusion schemes produce tilted concentration profiles for primary species, with higher concentrations near the surface and lower values at the top of the boundary layer, while TSM profiles yield more homogeneous concentrations in the planetary boundary layer (PBL). Ozone concentrations are also more homogeneous in the TSM PBL than in the diffusive PBL. Only deposition makes ozone concentrations slightly lower near the surface, while in diffusive case ozone is lower also due to titration by higher nitrogen oxide concentrations. The overall differences between the schemes remain small for ozone.Also, the development time and amplitude of an ozone city plume is not very sensitive to the choice of the mixing scheme. In the urban framework ozone build-up is slightly delayed by higher nitrogen oxide concentrations near the surface in the diffusive cases, but the plume development is similar to that of the TSM once the plume travels away from the emission area. Results also show that the sensitivity of ozone to nitrogen oxide and non-methane volatile organic compounds is itself not very sensitive to the mixing scheme.     

湿式纤维层非稳态过滤净化阻力的研究

在干式纤维层过滤净化阻力的理论基础上,提出清洗水均匀分布于纤维丝表面的基本假设,使湿式过滤中对液滴、液膜、液珠的分析简单具体化。并通过实验结论归纳出净化阻力随时间的变化规律,导出湿式纤维层非稳态过滤净化阻力的表达式,并用实验验证了其准确性。     

Toxicity of methyl tert-butyl ether to marine organisms: ambient water quality criteria calculation

In response to increasing concerns over the detection of methyl tert-butyl ether (MTBE) in groundwater and surface water and its potential effects in aquatic ecosystems, industry and the United States Environmental Protection Agency (USEPA) began to collaborate in 1997 to develop aquatic toxicity databases sufficient to derive ambient water quality criteria for MTBE consistent with USEPA requirements. Acute toxicity data for seven marine species, chronic toxicity data for an invertebrate, and plant toxicity data were developed to complete the saltwater database. The species tested were Cyprinodon variegatus, Gasterosteus aculeatus, Callinectes sapidus, Mytilus galloprovincialis, Palaemonetes pugio, Rhepoxynius abronius, Americamysis bahia, and Skeletonema costatum. The toxicity tests were conducted in accordance with USEPA and American Society for Testing and Materials testing procedures and Good Laboratory Practice guidelines. Data developed from this study were consistent with existing data and showed that MTBE has low acute and chronic toxicity to the marine species tested. Based upon measured MTBE concentrations, acute effects were found to range from 166 mg MTBE/l for the grass shrimp to 1950 mg MTBE/l for marine mussel. The no-observed effect concentration for the reproduction and growth of mysids was 26 mg MTBE/l during the life cycle test. The toxicity of MTBE to saltwater organisms is comparable to its toxicity to the freshwater species tested. Reported MTBE concentrations in coastal waters are several orders of magnitude lower than concentrations observed to cause effects in marine organisms.     

General features of the arctic relevant to climate change in freshwater ecosystems

Large variations exist in the size, abundance and biota of the two principal categories of freshwater ecosystems, lotic (flowing water; e.g., rivers, streams, deltas and estuaries) and lentic (standing water; lakes, ponds and wetlands) found across the circumpolar Arctic. Arctic climate, many components of which exhibit strong variations along latitudinal gradients, directly affects a range of physical, chemical and biological processes in these aquatic systems. Furthermore, arctic climate creates additional indirect ecological effects through the control of terrestrial hydrologic systems and processes, particularly those associated with cryospheric components such as permafrost, freshwater ice and snow accumulation/ablation. The ecological structure and function of arctic freshwater systems are also controlled by external processes and conditions, particularly those in the headwaters of the major arctic rivers and in the adjacent marine environment. The movement of physical, chemical and biotic components through the interlinked lentic and lotic freshwater systems are major determinants of arctic freshwater ecology.     

A three-layer diffusion-cell to examine bio-enhanced dissolution of chloroethene dense non-aqueous phase liquid

Microbial reductive dechlorination of trichloroethene (TCE) and perchloroethene (PCE) in the vicinity of their dense non-aqueous phase liquid (DNAPL) has been shown to accelerate DNAPL dissolution. A three-layer diffusion-cell was developed to quantify this bio-enhanced dissolution and to measure the conditions near the DNAPL interface. The 12 cm long diffusion-cell setup consists of a 5.5 cm central porous layer (sand), a lower 3.5 cm DNAPL layer and a top 3 cm water layer. The water layer is frequently refreshed to remove chloroethenes at the upper boundary of the porous layer, while the DNAPL layer maintains the saturated chloroethene concentration at the lower boundary. Two abiotic and two biotic diffusion-cells with TCE DNAPL were tested. In the abiotic diffusion-cells, a linear steady state TCE concentration profile between the DNAPL and the water layer developed beyond 21 d. In the biotic diffusion-cells, TCE was completely converted into cis-dichloroethene (cis-DCE) at 2.5 cm distance of the DNAPL. Dechlorination was likely inhibited up to a distance of 1.5 cm from the DNAPL, as in this part the TCE concentration exceeded the culture’s maximum tolerable concentration (2.5 mM). The DNAPL dissolution fluxes were calculated from the TCE concentration gradient, measured at the interface of the DNAPL layer and the porous layer. Biotic fluxes were a factor 2.4 (standard deviation 0.2) larger than abiotic dissolution fluxes. This diffusion-cell setup can be used to study the factors affecting the bio-enhanced dissolution of DNAPL and to assess bioaugmentation, pH buffer addition and donor delivery strategies for source zones.     

Effects of feed solutions on refuse hydrolysis and landfill leachate characteristics

Tap water, aerobically pre-treated leachate, and anaerobically pre-treated leachate, were each fed into the top of a series of three simulated landfills columns, filled with municipal solid waste collected in Shanghai, China. Changes in leachate, including pH, total organic carbon (TOC), and volatile fatty acids (VFAs), and the produced biogas were monitored over time. The tap-water-fed columns had a low hydrolysis rate that yielded an acidic environment (pH 4.8-5.4) in the leachate that inhibited methanogenesis reaction in the refuse. When aerobically pre-treated leachate was fed into the columns, the hydrolysis rate of total organic carbon fluctuated between 200 and 400 mg d-1 and methanogenesis in the refuse column was only partly activated. The hydrolysis rate of refuse fed with anaerobically pre-treated leachate was the highest among the three solutions. The high alkaline levels of the anaerobically pre-treated leachate and its methanogenic bacteria led to an early activation of methanogenesis in the refuse columns. The VFAs contributed approximately 40-60% of TOC in tap-water-fed columns, 60-80% of TOC in the columns fed aerobically pre-treated leachate, and up to 70-90% of TOC in columns fed with anaerobically pre-treated leachate. The feed solution had considerably affected leachate characteristics, and then the build-up of the methanogenesis in the refuse column and the composition of fermentation products in the leachate. The success of a bioreactor landfill depends on whether the recycled leachate could yield a favorable methanogenic environment in the top refuse layer, or whether an appropriate pre-treatment is adopted to modify the leachate characteristics.     

曝气对潜流人工湿地污染物沿程降解规律的影响

通过构建曝气及未曝气潜流人工湿地小试实验系统,研究曝气对人工湿地床体中污染物沿程变化规律的影响。实验结果表明,曝气对污染物沿程降解规律的影响与污染物种类有关,在净化COD和氨氮时,曝气人工湿地污染物主要以水平推流式降解为主,未曝气系统床体中则出现分层现象,深度为40 cm以上的床体区域中污染物以水平推流式降解为主,40 cm以下区域则以垂直梯度降解方式为主。对于磷来说,两对比系统均以水平推流降解方式为主,但不同深度上的降解速率有所差异,曝气系统30~50 cm的床体中间层降解速率较快,而未曝气系统50 cm以下的床体底层降解速率较快。将对比系统总体净化效果进一步比较发现,对于COD的去除来说,温度的影响大些,而对于氨氮和TP的去除来说,曝气的影响则更为显著。     

Risk assessment of herbicides and booster biocides along estuarine continuums in the Bay of Vilaine area (Brittany, France)

A 2-year study was implemented to characterize the contamination of estuarine continuums in the Bay of Vilaine area (NW Atlantic Coast, Southern Brittany, France) by 30 pesticide and biocide active substances and metabolites. Among these, 11 triazines (ametryn, atrazine, desethylatrazine, desethylterbuthylazine, desisopropyl atrazine, Irgarol 1051, prometryn, propazine, simazine, terbuthylazine, and terbutryn), 10 phenylureas (chlortoluron, diuron, 1-(3,4-dichlorophenyl)-3-methylurea, fenuron, isoproturon, 1-(4-isopropylphenyl)-3-methylurea, 1-(4-isopropylphenyl)-urea, linuron, metoxuron, and monuron), and 4 chloroacetanilides (acetochlor, alachlor, metolachlor, and metazachlor) were detected at least once. The objectives were to assess the corresponding risk for aquatic primary producers and to provide exposure information for connected studies on the responses of biological parameters in invertebrate sentinel species. The risk associated with contaminants was assessed using risk quotients based on the comparison of measured concentrations with original species sensitivity distribution-derived hazardous concentration values. For EU Water Framework Directive priority substances, results of monitoring were also compared with regulatory Environmental Quality Standards. The highest residue concentrations and risks for primary producers were recorded for diuron and Irgarol 1051 in Arzal reservoir, close to a marina. Diuron was present during almost the all survey periods, whereas Irgarol 1051 exhibited a clear seasonal pattern, with highest concentrations recorded in June and July. These results suggest that the use of antifouling biocides is responsible for a major part of the contamination of the lower part of the Vilaine River course for Irgarol 1051. For diuron, agricultural sources may also be involved. The presence of isoproturon and chloroacetanilide herbicides on some dates indicated a significant contribution of the use of plant protection products in agriculture to the contamination of Vilaine River. Concentration levels and associated risk were always lower in estuarine sites than in the reservoir, suggesting that Arzal dam reduces downstream transfer of contaminants and favors their degradation in the freshwater part of the estuary. Results of the additional monitoring of two tidal streams located downstream of Arzal dam suggested that, although some compounds may be transferred to the estuary, their impact was probably very low. Dilution by marine water associated with tidal current was also a major factor of concentration reduction. It is concluded that the highest risks associated to herbicides and booster biocides concerned the freshwater part of the estuary and that its brackish/saltwater part was exposed to a moderate risk, although some substances may sometimes exhibit high concentration but mainly at low tide and on an irregular basis.     

Comparative acute toxicity of organic pollutants and reference values for crustaceans. I. Branchiopoda, Copepoda and Ostracoda

The acute toxicity of 468 organic pollutants to planktonic crustaceans (Branchiopoda, Copepoda and Ostracoda) from pre-existing data was compared by means of statistical analysis and relative tolerance indices (Trel). A surrogate species commonly used in toxicity bioassays (Daphnia magna) showed toxicity levels--within one order of magnitude--similar to all other Cladocera species, at least for 82% of the chemicals studied. All neurotoxic insecticides except neonicotinoids, PCBs, organometallic compounds and PAHs are the most toxic substances to these organisms. Sensitivity levels among taxa were compared for individual chemicals as well as groups of chemicals with similar characteristics. Whilst there are marked differences in sensitivity among taxa and particular groups of chemicals, no consistent trends were found for freshwater and saltwater species in relation to the latter groups. No correlation between LC50 and size of these organisms was found other than by chance, making extrapolations based on allometric equations impossible.     

Freshwater systems and ecosystem services: Challenges and chances for cross-fertilization of disciplines

Freshwater ecosystems are among the most threatened in the world, while providing numerous essential ecosystem services (ES) to humans. Despite their importance, research on freshwater ecosystem services is limited. Here, we examine how freshwater studies could help to advance ES research and vice versa. We summarize major knowledge gaps and suggest solutions focusing on science and policy in Europe. We found several features that are unique to freshwater ecosystems, but often disregarded in ES assessments. Insufficient transfer of knowledge towards stakeholders is also problematic. Knowledge transfer and implementation seems to be less effective towards South-east Europe. Focusing on the strengths of freshwater research regarding connectivity, across borders, involving multiple actors can help to improve ES research towards a more dynamic, landscape-level approach, which we believe can boost the implementation of the ES concept in freshwater policies. Bridging these gaps can contribute to achieve the ambitious targets of the EU’s Green Deal.     

Persistent organochlorine levels in six prey species of the gyrfalcon Falco rusticolus in Iceland

Our previous investigations have revealed very high levels of organochlorines (OCs) in the Icelandic gyrfalcon Falco rusticolus, a resident top predator. We now examine six potential prey species of birds, both resident and migratory, in order to elucidate the most likely route of the OCs to the gyrfalcon. The ptarmigan Lagopus mutus, the most important prey of the gyrfalcon, contained very low levels of OCs. Bioaccumulation of polychlorinated biphenyls (PCBs) and DDTs in mallards Anas platyrhynchos, tufted ducks Aythya fuligula, golden plovers Pluvialis apricaria, purple sandpipers Calidris maritima, and black guillemots Cepphus grylle reflected their position in the foodchain. The differences in OC-levels seem nevertheless too high just to reflect the different food-chain levels of these species in Iceland. The winter grounds of the migratory golden plovers and tufted ducks appear to be more contaminated than the Icelandic terrestrial habitat of ptarmigans or the freshwater habitat as reflected in mallards, both resident species. However, spending the winter on the coast in Iceland, results in high levels of contaminants in purple sandpipers and black guillemots. Our results indicate OC contamination of the marine ecosystem in Iceland while the terrestrial and freshwater ecosystems are little affected. It is postulated that gyrfalcons receive the major part of the observed contamination from prey other than ptarmigan, especially birds associated with the marine ecosystem and also from migratory birds.     

Polychlorinated dibenzo-p-dioxin and dibenzofuran concentrations in common fish species in the Pearl River Delta area, China

Polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/Fs) concentrations in 31 fish samples from 19 commonly consumed freshwater and saltwater species from the Pearl River Delta Area were analyzed. The PCDD/Fs dietary intake from fish for the local population was evaluated to provide a database for setting the national PCDD/F limits in fish for the People's Republic of China. The median concentration from the 31 fish samples was 1.27 pg/g wet weight for the total of PCDD/Fs, and the median WHO-TEQ was 0.26 pg/g wet weight, and ranged from 0.063 to 1.30 pg WHO-TEQ/g wet weight. The dominant contributors to the WHO-TEQ were 1,2,3,7,8-PeCDD and 2,3,4,7,8-PeCDF, which accounted for 38% and 28%, respectively. The dietary intake of PCDD/Fs from fish for local people was estimated to be 0.47 pg WHO-TEQ/kg bw x day. In view of the findings, the dietary of PCDD/Fs from other foods of animal origins in China should be studied in more detail as soon as possible in order that standards can be put forward to protect human health.     

Adsorption-desorption,persistence, and leaching behavior of dithiopyr in an alluvial soil of India

Investigations were undertaken to determine the adsorption-desorption, persistence and leaching of dithiopyr (S,S'-dimethyl 2-difluoromethyl-4-isobutyl-6-trifluoromethyl pyridine-3,5-dicarbothioate) in an alluvial soil under laboratory condition. The adsorption-desorption studies were carried out using batch equilibration technique. The mass balance studies showed that 83-97% of the pesticide was recovered during adsorption-desorption studies. The results revealed strong adsorption of dithiopyr in alluvial soil with Kd values ranging from 3.97-5.78 and Freundlich capacity factor (KF) value of 2.41. The strong adsorption was evident from the hysteresis effect observed during desorption. The hysteresis coefficients ranged from 0.17-0.40. The persistence studies were carried out at two concentrations (1.0 and 10.0 microg g(-1) level) under field capacity moisture and submerged condition by incubating the treated soil at 25 +/- 1 degrees C. In general, dithiopyr persisted beyond 90 days with half-life varying from 11.5-12.9 days under different conditions. The rate of application and moisture regimes had no overall effect on the persistence. The leaching studies carried out in packed column under saturated flow condition revealed that dithiopyr was highly immobile in alluvial soil. Only small amounts (0.02-0.04%) were recovered from leachate whereas major portion (99.9%) remained in top layer of the soil column. The data suggest that strong adsorption of dithiopyr will cause a greater persistence problem in the soil. However, the chances of its movement to ground water will be negligible due to its immobility.     

Spatial distribution and source apportionment of PCBs in sediments around İzmit industrial complexes, Turkey

The spatial distribution, degree of pollution and major sources of PCBs were evaluated in surficial sediments within the heavily urbanized and industrialized ?zmit Bay and its main freshwater inputs. ΣPCB concentrations range from 2.90 to 85.4ngg(-1) in marine sediments and from ND to 47.7ngg(-1) in freshwater sediments. Results suggest that high concentrations of ΣPCBs were localized around a chlor-alkali plant and an industry that handles bulk liquid, dry and drummed chemicals, and petroleum products in the Bay. Using a chemical mass balance receptor model (CMB), major sources of PCBs in the region were investigated. The CMB model identified Aroclor 1254 and 1260 to be the major PCB sources in marine sediments and the less chlorinated Aroclor 1248 and 1242 as the major PCB sources in freshwater sediments. The potential sources for the PCBs were briefly discussed in terms of their use in various industrial applications.