A new direct thermal desorption-GC/MS method: Organic speciation of ambient particulate matter collected in Golden, BC

Particulate matter having an aerodynamic diameter less than 2.5 μm (PM2.5) is thought to be implicated in a number of medical conditions, including cancer, rheumatoid arthritis, heart attack, and aging. However, very little chemical speciation data is available for the organic fraction of ambient aerosols. A new direct thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) method was developed for the analysis of the organic fraction of PM2.5. Samples were collected in Golden, British Columbia, over a 15-month period. n-Alkanes constituted 33–98% by mass of the organic compounds identified. PAHs accounted for 1–65% and biomarkers (hopanes and steranes) 1–8% of the organic mass. Annual mean concentrations were: n-alkanes (0.07–1.55 ng m⁻³), 16 PAHs (0.02–1.83 ng m⁻³), and biomarkers (0.02–0.18 ng m⁻³). Daily levels of these organics were 4.89–74.38 ng m⁻³, 0.27–100.24 ng m⁻³, 0.14–4.39 ng m⁻³, respectively. Ratios of organic carbon to elemental carbon (OC/EC) and trends over time were similar to those observed for PM2.5. There was no clear seasonal variation in the distribution of petroleum biomarkers, but elevated levels of other organic species were observed during the winter. Strong correlations between PAHs and EC, and between petroleum biomarkers and EC, suggest a common emission source – most likely motor vehicles and space heating.     

Volatilization characteristics of organic solutes in stirred solution

The effects of turbulence intensity (velocity gradient, G (s⁻¹)), Henry's law constant (H), and molecular weight (M) on the volatilization rates of organic compounds are examined using changes in the mass transfer coefficients (K_OL (cm/min)) under specific liquid-mixing intensities. The selected compounds were divided into three groups according to their H values (mole in gas/mole in liquid, dimensionless), which ranged from 10² to 10⁻⁵. The relationship of the K_OL relative to G, H and M was obtained via multiple regression. The obtained values of these parameters indicate that the primary factor affecting the K_OL values of the high H compounds is their M values. The effects of the H values on the K_OL values of the high H compounds can be neglected. On the other hand, the H value is the major factor determining the K_OL values of the low H compounds. The changes in the K_OL values of the different H compounds exhibit different profiles as the liquid-mixing intensity increases. The M and H values of middle H compounds possibly affect their K_OL values. The effects of the liquid-mixing intensity on the K_OL values of the organic compounds increase with increasing H values. The variation in the K_OL values might be a result of the concentration of the organic compounds at the interface between the liquid and gas films. The empirical relationship between K_OL and some selected parameters, G, H and M, is examined in this study. The obtained results can help to estimate volatilization loss of organic solutes in wastewater treatment facilities.     

Effects of dredging on benthic diatom assemblages in a lowland stream

The objective of this study was to assess the effects of dredging on the structure and composition of diatom assemblages from a lowland stream and to investigate whether the response of diatom assemblages to the dredging is also influenced by different water quality. Three sampling sites were established in Rodríguez Stream (Argentina); physico-chemical variables and benthic diatom assemblages were sampled weekly in spring 2001. Species composition, cell density, diversity and evenness were estimated. Diatom tolerance to organic pollution and eutrophication were also analyzed. Differences in physico-chemical variables and changes in benthic diatom assemblages were compared between the pre- and post-dredging periods using a t-test. Data were analyzed using Principal Components Analysis (PCA), non-metric multidimensional scaling (MDS) ordination and cluster analysis. The effects of dredging in the stream involve two types of disturbances: (i) in the stream bed, by the removal and destabilization of the substrate and (ii) in the water column, by generating chemical changes and an alteration of the light environment of the stream. Suspended solids, soluble reactive phosphorus and dissolved inorganic nitrogen were significantly higher in post-dredging periods. Physical and chemical modifications in the habitat of benthic diatoms produced changes in the assemblage; diversity and species numbers showed an immediate increase after dredging, decreasing at the end of the study period. Changes in the tolerance of the diatom assemblage to organic pollution and eutrophication were also observed as a consequence of dredging; in the post-dredging period sensitive species were replaced by either tolerant or most tolerant species. These changes were particularly noticeable in site 1 (characterized by its lower amount of nutrients and organic matter previous to dredging), which showed an increase in the amount of nutrients and oxygen demand as a consequence of sediment removal. However, these changes were not so conspicuous in sites 2 and 3, which already presented a marked water quality deterioration before the execution of the dredging works.     

Field Trial Assessment of Biological,Chemical, and Physical Responses of Soil to Tillage Intensity,Fertilization, and Grazing

Soil microbial populations can fluctuate in response to environmental changes and, therefore, are often used as biological indicators of soil quality. Soil chemical and physical parameters can also be used as indicators because they can vary in response to different management strategies. A long-term field trial was conducted to study the effects of different tillage systems (NT: no tillage, DH: disc harrow, and MP: moldboard plough), P fertilization (diammonium phosphate), and cattle grazing (in terms of crop residue consumption) in maize (Zea mays L.), sunflower (Heliantus annuus L.), and soybean (Glycine max L.) on soil biological, chemical, and physical parameters. The field trial was conducted for four crop years (2000/2001, 2001/2002, 2002/2003, and 2003/2004). Soil populations of Actinomycetes, Trichoderma spp., and Gliocladium spp. were 49% higher under conservation tillage systems, in soil amended with diammonium phosphate (DAP) and not previously grazed. Management practices also influenced soil chemical parameters, especially organic matter content and total N, which were 10% and 55% higher under NT than under MP. Aggregate stability was 61% higher in NT than in MP, 15% higher in P-fertilized soil, and also 9% higher in not grazed strips, bulk density being 12% lower in NT systems compared with MP. DAP application and the absence of grazing also reduced bulk density (3%). Using conservation tillage systems, fertilizing crops with DAP, and avoiding grazing contribute to soil health preservation and enhanced crop production.     

Binding of polycyclic aromatic hydrocarbons by humic acids formed during composting

Binding of two model polycyclic aromatic hydrocarbons (PAHs), phenanthrene and pyrene, by humic acids (HAs) isolated from an organic substrate at different stages of composting and a soil was investigated using a batch fluorescence quenching method and the modified Freundlich model. With respect to soil HA, the organic substrate HA fractions were characterized by larger binding affinities for both phenanthrene and pyrene. Further, isotherm deviation from linearity was larger for soil HA than for organic substrate HAs, indicating a larger heterogeneity of binding sites in the former. The composting process decreased the binding affinity and increased the heterogeneity of binding sites of HAs. The changes undergone by the HA fraction during composting may be expected to contribute to facilitate microbial accessibility to PAHs. The results obtained also suggest that bioremediation of PAH-contaminated soils with matured compost, rather than with fresh organic amendments, may result in faster and more effective cleanup.     

Nanofiltration of concentrated and salted tuna cooking juices

Tuna cooking juice from a Tunisian tuna-processing unit has a high level of polluting load: chemical oxygen demand (COD) is comprised between 4 and 20 g L⁻¹, nitrogen kjedahl (NK) between 0.6 and 3 g L⁻¹ and dry matter between 120 and 160 g L⁻¹. The juice has thus to be treated before being rejected into the environment. This paper considers the nanofiltration (NF) of these concentrated organic/inorganic mixtures using an AFC 30 (NF) membrane. The work focusses on the effect of organic and inorganic matters on the permeate flux and rejections of these matters. For this purpose, mixtures of salt and organic pollution (COD), used as model solutions, were prepared by the dilution of a typical industrial tuna cooking juice. The permeate flux was found to decrease when salt and organic matter concentrations increase. The recovery rate in organic matter decreases with increasing salt or organic matter content and the recovery rate of salt decreases when the COD concentration increases.     

武汉地区水环境中全氟化合物污染水平及其分布特征

武汉作为中国氟化工行业的主要生产基地之一,其水环境中全氟及多氟类化合物(PFASs)污染情况对评估该地区水环境生态安全至关重要。采集了武汉城区10个污水处理厂进、出口污水和19个地表水样品,利用HPLC-ESI-MS/MS技术分析研究该区域水环境中PFASs污染水平及其分布特征。结果发现,武汉地区的污水和地表水样品中,PFASs污染均以短链同系物全氟丁酸(PFBA)和全氟丁基磺酸(PFBS)为主。污水处理厂进、出口污水中PFASs总浓度分别为11.8~12 700 ng·L~(-1)和19.1~9 970 ng·L~(-1)。在城区15个湖水样品中,PFASs总浓度为21.0~10 900 ng·L~(-1);在流经城区的4个江水样品中,PFASs总浓度为4.11~4.77 ng·L~(-1),比湖水样品中PFASs浓度水平低1~2个数量级。与污水中PFASs空间分布趋势一致,各湖泊水样中PFASs总体水平呈现汉口汉阳武昌的趋势,表明城市工业布局与人口密度程度直接影响城市PFASs污染空间分布。值得注意的是,与以往水环境中PFASs污染以全氟辛酸(PFOA)和全氟辛基磺酸(PFOS)为主不同,武汉地区水环境中PFASs污染以短链同系物为主,表明短链替代效应已经渐渐在中国化工领域出现,中国全氟行业在响应国际组织规范和建议的基础上做出了实质性进展。然而,对于短链PFASs的污染特征、迁移运输以及生态风险等科学问题,还需要更进一步的研究。     

Influence of dissolved humic substances on the mass transfer of organic compounds across the air-water interface

The effect of dissolved humic substances (DHS) on the rate of water-gas exchange of two volatile organic compounds was studied under various conditions of agitation intensity, solution pH and ionic strength. Mass-transfer coefficients were determined from the rate of depletion of model compounds from an apparatus containing a stirred aqueous solution with continuous purging of the headspace above the solution (dynamic system). Under these conditions, the overall transfer rate is controlled by the mass-transfer resistance on the water side of the water-gas interface. The experimental results show that the presence of DHS hinders the transport of the organic molecules from the water into the gas phase under all investigated conditions. Mass-transfer coefficients were significantly reduced even by low, environmentally relevant concentrations of DHS. The retardation effect increased with increasing DHS concentration. The magnitude of the retardation effect on water-gas exchange was compared for Suwannee River fulvic and humic acids, a commercially available leonardite humic acid and two synthetic surfactants. The observed results are in accordance with the concept of hydrodynamic effects. Surface pressure forces due to surface film formation change the hydrodynamic characteristics of water motion at the water-air interface and thus impede surface renewal.     

Chlorinated solvents in a petrochemical wastewater treatment plant: an assessment of their removal using self-organising maps

The self-organising map approach was used to assess the efficiency of chlorinated solvent removal from petrochemical wastewater in a refinery wastewater treatment plant. Chlorinated solvents and inorganic anions (11 variables) were determined in 72 wastewater samples, collected from three different purification streams. The classification of variables identified technical solvents, brine from oil desalting and runoff sulphates as pollution sources in the refinery, affecting the quality of wastewater treatment plant influent. The classification of samples revealed the formation of five clusters: the first three clusters contained samples collected from the drainage water, process water and oiled rainwater treatment streams. The fourth cluster consisted mainly of samples collected after biological treatment, and the fifth one of samples collected after an unusual event. SOM analysis showed that the biological treatment step significantly reduced concentrations of chlorinated solvents in wastewater.     

Identification of relevant micropollutants in Austrian municipal wastewater and their behaviour during wastewater treatment

The European Union has defined environmental quality standards (EQSs) for surface waters for priority substances and several other pollutants. Furthermore national EQSs for several chemicals are valid in Austria. The study investigated the occurrence of these compounds in municipal wastewater treatment plant (WWTP) effluents. In a first screening of 15 WWTPs relevant substances were identified, which subsequently were monitored in 9 WWTPs over 1 year (every 2 months). Out of 77 substances or groups of substances (including more than 90 substances) 13 were identified as potentially relevant in respect to water pollution and subjected to the monitoring, whereas most other compounds were detected in concentrations far below the respective EQS for surface waters and therefore not further considered. The preselected 13 compounds for monitoring were cadmium (Cd), nickel (Ni), copper (Cu), selenium (Se), zinc (Zn), diuron, polybrominated diphenyl ethers (PBDEs), di(ethyl-hydroxyl)phthalate (DEHP), tributyltin compounds (TBT), nonylphenoles (NP), adsorbable organic halogens (AOX) and the complexing agents ethylenediaminetetraacetic acid (EDTA) as well as nitrilotriacetic acid (NTA). In the effluents of WWTPs the concentrations of the priority substances Cd, NP, TBT and diuron frequently exceeded the respective EQS, whereas the concentrations for DEHP and Ni were below the respective EQS. The effluent concentrations for AOX, EDTA, NTA, Cu, Se and Zn frequently are in the range or above the Austrian EQS for surface waters. Besides diuron and EDTA all compounds are removed at least partially during wastewater treatment and for most substances the removal via the excess sludge is the major removal pathway. For the 13 compounds which were monitored in WWTP effluents population equivalent specific discharges were calculated. Since for many compounds no or only few information is available, these population equivalent specific discharges can be used to assess emissions from municipal WWTPs to surface waters as well as to make a first assessment of the impact of a discharge on surface waters chemical status. Comparing discharges and river pollution on a load basis, the influence of diffuse sources becomes obvious and therefore should also be taken into consideration in river management.