Monofluorinated analogues of polychlorinated biphenyls (F-PCBs): synthesis using the Suzuki-coupling, characterization, specific properties and intended use

An improved method, a palladium-catalyzed cross-coupling reaction the so-called Suzuki-coupling, was used to synthesize 19 monofluorinated analogues (F-PCBs) of polychlorinated biphenyls (PCBs), including analogues of PCBs 28, 52 and 81. The coupling of chlorinated and/or fluorinated isomers of aryl boronic acids with bromo- and/or iodobenzenes gave the desired F-PCB congeners in good to excellent yields. The self-coupling product of the aryl boronic acids was the major impurity, but this limitation could be minimized. The influence of ortho-substitution by chlorine on the reaction time was studied in detail. The F-PCBs were characterized by means of ¹H and ¹⁹F NMR and mass spectrometry (MS). F-PCBs show remarkably similar characteristics in many aspects to those of the corresponding non-fluorinated parent PCBs. Since fluorine is generally resistant to degradation, once incorporated into a substrate it functions as an indelible label that can be used to monitor structures and dynamics. F-PCBs may prove their usefulness as markers and tracers in mechanistic and toxicological studies. The aim of further research will be to test the suitability of fluorine as a sensitive probe in a broad range of applications, including synthesis, analytical, mechanistic and toxicological studies.     

Evaluation of resin and fatty acid concentration levels by online sample enrichment followed by atmospheric pressure chemical ionization-mass spectrometry (APCI-MS)

Background, aim, and scope  In papermaking, there is a continuous interest both to minimize fresh water consumption and to reduce discharges into the environment. These general trends mean an increase in the amounts of detrimental substances, such as resin and fatty acids, in papermaking process waters. Resin acids, in particular, are responsible for much of the toxicity typically present in paper mill effluents and, for this reason, the routine and rapid monitoring of these compounds in various process streams is necessary. This also means that there is a continuous need to develop straightforward offline and online techniques to clarify problems occurring, for example, as a result of the introduction of more intensively closed systems of water circulation. In the present study, we describe the use of a novel, online, sample enrichment technique followed by atmospheric pressure chemical ionization–mass spectrometry (APCI-MS) suitable for monitoring the concentration levels of common resin and fatty acids in papermaking process waters. Materials and methods  The representative process water samples were taken from the grinding zone of a thermomechanical pulping mill. The samples were first preconcentrated in a precolumn C18, and the analytes were transferred online to MS. The high intensive [M–H]⁻ ion was used for the identification of each analyte since, according to the present ionization method, no other fragmentation was observed. Laboratory-scale, online measurements with an online sample feed were carried out by connecting a centrifugal pump and a ceramic filter to the APCI-MS. Results  Quality parameters, such as repeatability, linearity, and limit of detection (LOD), were determined by using dehydroabietic acid (DHAA) in order to evaluate the suitability of the method for the rapid screening of concentration levels. This method provided satisfactory linearity and a good correlation between analyte concentration and peak area. The suitability of the system for the continuous analysis of the same acids was evaluated in laboratory-scale, online experiments. In all cases, the response to changes in the analyte concentration was linear, and the repeatability of the system was also satisfactory. Discussion  Only a few studies have been published on the analysis of resin and fatty acids with MS techniques. The present method was applied to the monitoring of dehydroabietic, oleic, and stearic acids. The quality parameters were highly comparable with those reported earlier, and the LOD values of the DHAA were below the levels usually encountered in process waters. The quality parameters were only slightly higher than those obtained by the traditional methods of analysis, probably due to the absence of an effective sample clean-up before analysis. Conclusions  The results of the laboratory-scale, online experiments indicated that the online enrichment APCI-MS system is a suitable alternative for monitoring the concentration levels of selected resin and fatty acids in papermaking process waters. The method can be used, for example, to provide useful information about the concentration levels of these acids in different stages of the process, thus signaling possibly impending problems. In general, faster and simpler measurements are needed to meet the requirements for a reduction in fresh water usage in papermaking. Recommendations and perspectives  Compared to the conventional methods used for this purpose, the main benefits of the method are rapidity of measurement, simplicity of use, and absence of the need for multistage sample treatments (short analysis time). For this reason, this online method is more suitable for the control of papermaking by analyzing the concentration levels of interfering substances (i.e., selected resin and fatty acids) than an offline analysis detailing all the individual extractives-based compounds in process streams. It is also obvious that the technique can easily be modified for other environmental pollutants as well.     

Mercury mass balance study in Wujiangdu and Dongfeng Reservoirs, Guizhou, China

From October 2003 to September 2004, we conducted a detailed study on the mass balance of total mercury (THg) and methylmercury (MeHg) of Dongfeng (DF) and Wujiangdu (WJD) reservoirs, which were constructed in 1992 and 1979, respectively. Both reservoirs were net sinks for THg on an annual scale, absorbing 3319.5 g km⁻² for DF Reservoir, and 489.2 g km⁻² for WJD Reservoirs, respectively. However, both reservoirs were net sources of MeHg to the downstream ecosystems. DF Reservoir provided a source of 32.9 g MeHg km⁻² yr⁻¹, yielding 10.3% of the amount of MeHg that entered the reservoir, and WJD Reservoir provided 140.9 g MeHg km⁻² yr⁻¹, yielding 82.5% of MeHg inputs. Our results implied that water residence time is an important variable affecting Hg methylation rate in the reservoirs. Our study shows that building a series of reservoirs in line along a river changes the riverine system into a natural Hg methylation factory which markedly increases the %MeHg in the downstream reservoirs; in effect magnifying the MeHg buildup problem in reservoirs.     

Arsenic and Mn levels in Isaza (Gymnogobius isaza) during the mass mortality event in Lake Biwa, Japan

The present study measured the concentrations of 25 elements (Li, Mg, V, Cr, Mn, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, Hg, Tl, Pb and Bi) in the whole body of Isaza which is an endemic fish species to Lake Biwa, Japan, and compared the values in the specimens from the mass mortality Isaza (MMI) and normal fresh Isaza (NFI). The mean levels of Mn and total As (T-As) were relatively higher in MMI than in NFI. In the T-As, highly toxic inorganic As was detected in MMI. Moreover we found Mn and As concentrations in surface sediment were extremely high and temporally increased. From all these results, we could infer that the dissolution of Mn and As from surface sediment of Lake Biwa might have been one of the cause for the mass mortality of Isaza.     

Wastewater reuse in Mediterranean semi-arid areas: The impact of discharges of tertiary treated sewage on the load of polar micro pollutants in the Llobregat river (NE Spain)

The presence of sewage-borne micro contaminants in environmental waters is directly related to the discharge of treated effluents from wastewater treatment plants (WWTP) and the flow rate of the receiving river waters. Mediterranean rivers, in particular, are characterized by important fluctuations in the flow rates and heavy pollution pressures resulting from extensive urban, industrial and agricultural activities. This translates into contamination levels in these rivers often higher than those in other larger European basins. The present work provides an overview of the occurrence of five groups of organic contaminants (131 compounds) namely pharmaceuticals, illicit drugs, polar pesticides, estrogens, alkylphenols and related ethoxylates in WWTP tertiary treatment effluents. Data gathered during a period of water reuse carried out in the lower stretch of the Llobregat river (NE Spain), in the surroundings of the town of Barcelona as a consequence of the severe drought that took place along the years 2007-2008 are presented as illustrative example. In general, measured concentrations of the target compounds were in the low to mid ng L⁻¹ range. The total concentration of each compound class downstream to the discharge point was similar or slightly higher than that found upstream. Regarding the loads calculated for each compound, the relative contribution from the river upstream and the tertiary effluent were highly compound depending with no apparent trend. However, estimation of the overall bulk loads for each compound class determined in the Llobregat river showed the following rank order: pharmaceuticals > alkylphenols > pesticides > illicit drugs ? estrogens.     

PTR-MS measurements and analysis of models for the calculation of Henry's law constants of monosulfides and disulfides

Sulfides are known for their strong odor impact even at very low concentrations. Here, we report Henry’s law constants (HLCs) measured at the nanomolar concentration range in water for monosulfides (dimethylsulfide, ethylmethylsulfide, diethylsulfide, allylmethylsulfide) and disulfides (dimethyldisulfide, diethylsulfide, dipropylsulfide) using a dynamic stripping technique coupled to Proton Transfer Reaction-Mass Spectrometry (PTR-MS). The experimental data were compared with literature values and to vapor/solubility calculations and their consistency was confirmed employing the extra-thermodynamic enthalpy-entropy compensation effect. Our experimental data are compatible with reported literature values, and they are typically lower than averaged experimental literature values by about 10%. Critical comparison with other freely available models (modeled vapor/solubility; group and bond additivity methods; Linear Solvation Energy Relationship; SPARC) was performed to validate their applicability to monosulfides and disulfides. Evaluation of theoretical models reveals a large deviation from our measured values by up to four times (in units of M atm⁻¹). Two group contribution models were adjusted in view of the new data, and HLCs for a list of sulfur compounds were calculated. Based on our findings we recommend the evaluation and adaption of theoretical models for monosulfides and disulfides to lower values of solubility and higher values of fugacity.     

Behaviour of arsenic in forested catchments following a high-pollution period

Due to high availability of adsorption sites, forested catchments could be net sinks for pollutant arsenic both during the period of increasing and decreasing pollution. We tested this hypothesis along a north-south pollution gradient in spruce die-back affected areas of Central Europe. For two water years (2007-2008), we monitored As fluxes via spruce-canopy throughfall, open-area precipitation, and runoff in four headwater catchments (Czech Republic). Since 1980, atmospheric As inputs decreased 26 times in the north, and 13 times in the south. Arsenic export by runoff was similar to atmospheric inputs at three sites, resulting in a near-zero As mass balance. One site exhibited a net export of As (2.2 g ha⁻¹ yr⁻¹). In contrast, the preceding period (1995-2006) showed much higher As fluxes, and higher As export. Czech catchments do not serve as net sinks of atmospheric As. A considerable proportion of old industrial arsenic is flushed out of the soil.     

Grain size partitioning of platinum-group elements in road-deposited sediments: implications for anthropogenic flux estimates from autocatalysts

Twelve road-deposited sediment samples were analyzed for platinum-group elements (PGEs) and Pb in the <63 microm fraction of an urban watershed in Hawaii. Three samples were further fractionated into five size classes, from 63-125 microm to 1000-2000 microm, and these were analyzed for PGEs and Pb. Concentrations in the <63 microm fraction reached 174 microg/kg (Pt), 101 microg/kg (Pd), 16 microg/kg (Rh), and 1.3 microg/kg (Ir). Enrichment ratios followed the sequence Rh>Pt=Pd>Ir. Iridium was geogenic in origin, while the remaining PGEs indicated significant anthropogenic contamination. Palladium, Pt and Rh concentrations and enrichment signals were consistent with PGE bivariate ratios and PGE partitioning in three-way catalysts. Size partitioning indicated that the <63 microm fraction had the lowest PGE concentrations and mass loading percentages. These data suggest that autocatalyst PGE flux estimates into the environment will be significantly underestimated if only a fine grain size fraction is analyzed.     

A pragmatic approach for estimation of source-zone emissions at LNAPL contaminated sites

When considering natural attenuation as a remediation strategy at a site contaminated by a light non-aqueous phase liquid (LNAPL), it is important to consider the emission of contaminants from the source zone. A quantification of source-zone emissions is essential both for comparison with down-gradient mass fluxes to provide an estimate of fractional mass flux reduction, as well as for estimating the source lifetime. Because the spatial distribution of LNAPL at a field site is strongly dependent on both the spill circumstances and the heterogeneity of the geologic materials, which can be problematic for in-situ determination, alternative methods for estimating source-zone emissions are needed. In this work, a three-dimensional multiphase flow and transport modelling approach is used to investigate the relationship between the lateral extent of an LNAPL body and the emission of contaminants to groundwater at a contaminated site. For simulations involving an LNAPL release in an aquifer comprised of heterogeneous porosity and permeability distributions that were generated geostatistically, it is shown that a simple linear relationship exists between the lateral extent of the LNAPL body in the capillary fringe and the emission to the aqueous phase. The parameters describing the relationship are found to be linear functions of the groundwater flow velocity and the vertical infiltration rate. This site-specific relationship provides a simple method to estimate contaminant emissions to groundwater at LNAPL contaminated sites.     

大跨人行过街天桥利用MTMD减振控制的理论分析

大跨人行天桥的自振频率通常比较低,与人行走时的频率接近,因此行人通过天桥时容易产生竖向共振,影响天桥的正常使用。本文研究多重调谐质量阻尼(MTMD)系统对大跨人行过街天桥竖向振动的控制作用,首先建立起天桥-MTMD系统的分析模型,推导出系统的传递函数及动力放大系数的数学表达式,继而分析了TMD的数量、阻尼比和频带宽等参数对结构的动力放大系数的影响,为实际工程结构设计MTMD减振系统时提供参考。以沈阳某大跨人行天桥为例,进行MTMD优化设置后,能有效减小天桥的受迫振动和自由振动,从而将振动控制在人体的舒适度范围之内。