The role of forest type in the variability of DOC in atmospheric deposition at forest plots in Italy

Dissolved organic carbon (DOC) was studied in atmospheric deposition samples collected on a weekly basis in 2005-2009 at 10 forest plots in Italy. The plots covered a wide range of geographical attributes and were representative of the main forest types in Italy. Both spatial and temporal variations in DOC concentrations and fluxes are discussed, with the aim of identifying the main factors affecting DOC variability. DOC concentration increased from bulk to throughfall and stemflow water samples at all sites, as an effect of leaching from leaves and branches, going from 0.7-1.7 mg C L(-1) in bulk samples to 1.8-15.8 mg C L(-1) in throughfall and 4.2-10.7 mg C L(-1) in stemflow, with striking differences among the various plots. Low concentrations were found in runoff (0.5-2.0 mg C L(-1)), showing that the export of DOC via running waters was limited. The seasonality of DOC in throughfall samples was evident, with the highest concentration in summer when biological activity is at a maximum, and minima in winter due to limited DOC production and leaching. Statistical analysis revealed that DOC had a close relationship with organic and total nitrogen, and with nutrient ions, and a negative correlation with precipitation amount. Forest type proved to be a major factor affecting DOC variability: concentration and, to a lesser extent, fluxes were lower in stands dominated by deciduous species. The character of evergreens, and the size and shape of their leaves and needles, which regulate the interception mechanism of dry deposition, are mainly responsible for this.     

Toxic equivalency factors for PAH and their applicability in shellfish pollution monitoring studies

Fish and shellfish are exposed to a wide range of polycyclic aromatic hydrocarbons (PAH) following oil spills at sea, and can become contaminated as a result. Finfish have a more effective mixed-function oxidase enzyme system than shellfish, and are therefore able to metabolise and excrete PAH more effectively than the invertebrates. Thus, contamination by high-molecular weight PAH, including those with carcinogenic potential and so of concern with regard to human consumers, is therefore usually observed in shellfish, and particularly in bivalve molluscs. Oil spills are not the sole source of PAH, however, as parent compounds are also generated by a wide range of combustion processes. In this paper, consideration is given to monitoring data gathered following recent oil spills (both of crude oil and diesel fuel), alongside data from other studies. These include studies conducted around a former gasworks site and downstream of an aluminium smelter in the UK, and from mussel monitoring studies undertaken in the UK and the USA (including the Exxon Valdez oil spill and the National Status and Trends programme), and in other countries in Europe. For comparative purposes the PAH concentrations are summed and also expressed as benzo[a]pyrene equivalents, their relative concentrations being weighted in relation to the carcinogenic potential of individual PAH compounds using toxic equivalency factors (TEF). Our aim was to assess the utility of this approach in fishery resource monitoring and control following oil spills. Certainly this approach seems useful from the data assessed in this study. and the relative ranking of the various studies seems to reflect the relative degree of concern for human consumers due to the differing contamination sources. As a simple tool for control purposes it is equally applicable to PAH derived from oil spills, and from industrial and combustion sources.     

Relative Phytoplankton growth responses to physically and chemically dispersed South Louisiana sweet crude oil

We conducted controlled laboratory exposure experiments to assess the toxic effects of water-accommodated fractions (WAFs) of South Louisiana sweet crude oil on five phytoplankton species isolated from the Gulf of Mexico. Experiments were conducted with individual and combinations of the five phytoplankton species to determine growth inhibitions to eight total petroleum hydrocarbon (TPH) equivalent concentrations ranging from 461 to 7,205 ppb. The composition and concentration of crude oil were altered by physical and chemical processes and used to help evaluate crude oil toxicity. The impact of crude oil exposure on phytoplankton growth varied with the concentration of crude oil, species of microalgae, and their community composition. At a concentration of TPH <?1,200 ppb, dinoflagellate species showed significantly better tolerance, while diatom species showed a higher tolerance to crude oil at higher concentrations of TPH. For both groups, the larger species were more tolerant to crude oil than smaller ones. The toxicity potential of crude oil seems to be strongly influenced by the concentration of polycyclic aromatic hydrocarbons (PAHs). The addition of the dispersant, Corexit® EC9500A, increased the amount of crude oil up to 50-fold in the water column, while the physical enhancement (vigorous mixing of water column) did not significantly increase the amount of TPH concentration in the water column. The species response to crude oil was also examined in the five-species community. Each phytoplankton species showed considerably less tolerance to crude oil in the five-species community compared to their individual responses. This study provides baseline information about individual phytoplankton responses to crude oil and dispersed crude oil for subsequent research efforts seeking to understand the impacts of oil on the phytoplankton in the bigger picture.     

溶解性有机碳对微库仑法测定水中可吸附有机卤素的影响

微库仑法测水样中可吸附有机卤素(AOX)受多种因素影响,其中溶解性有机碳(DOC)的影响非常显著。DOC对微库仑法2种前处理方法(双柱法和振荡法)的影响差异很大。双柱法受DOC影响较小,当DOC浓度小于1 000 mg/L时,AOX加标回收率范围为94.0%~104%。振荡法受DOC影响较明显,随着DOC浓度的升高,AOX回收率持续下降,当DOC浓度达到1 000 mg/L时,AOX加标回收率下降至72.1%,但DOC浓度小于100 mg/L时,AOX加标回收满足方法要求。进一步研究发现,DOC对振荡法的影响主要由于竞争吸附降低了活性炭对AOX的吸附容量,而非吸附速率,虽然增大活性炭用量可在一定程度上减小DOC对AOX测定的影响,但对样品进行稀释是减少DOC影响的最简单高效的办法。同时,DOC对不同类型的有机卤代物影响不同,有机溴受DOC影响程度小于有机氯。     

Predicting bioaccumulation of PAHs in the trophic chain in the estuary region of Paranagua, Brazil

The presence of polycyclic aromatic hydrocarbon (PAH) compounds in sediment and water samples collected in the estuary area of Paranagua, southern Brazil, was investigated. There is a lot of port activity in the region. Recreational fishing is widespread; thus, there is concern about possible contamination by PAHs. The 16 priority PAHs were investigated, and only eight were found. The total concentration of PAHs ranged from 40.8 to 406.8 ng/g. High molecular weight were the most abundant, while PAHs with a low molecular weight were absent. There are suspicions that the main source of PAHs is combustion, but some uncertainties exist, and there may even be the presence of PAHs resulting from accidental spills of crude oil. Although the sediments contain PAHs, the amount is below the maximum concentrations allowed by the Brazilian environmental legislation, as well as the maximum levels at which adverse effects are observed. From the analytical results, a probable bioaccumulation was assessed in the local trophic chain using a mathematical model (Arnot and Gobas, Environ Toxicol Chem 23(10):2343?C2355, 2004). The model showed that there is a possibility of biomagnification along the food chain selected. Three fishes with high local consumption were selected, and the concentration of some PAHs could be found in those fishes.     

Atmospheric BTEX concentrations in the vicinity of the crude oil refinery of the Baltic region

Among chemical industries, petroleum refineries have been identified as large emitters of a wide variety of pollutants. Benzene, toluene, ethylbenzene, and xylene (BTEX) form an important group of aromatic volatile organic compounds (VOCs) because of their role in the troposphere chemistry and the risk posed to human health. A very large crude oil refinery of the Baltic States (200,000 bbl/day) is situated in the northern, rural part of Lithuania, 10 km from the town of Ma?eikiai (Lithuania). The objectives of this study were: (1) to determine of atmospheric levels of BTEX in the region rural and urban parts at the vicinity of the crude oil refinery; and (2) to investigate the effect of meteorological parameters (wind speed, wind direction, temperature, pressure, humidity) on the concentrations measured. The averaged concentration of benzene varied from 2.12 ppbv in the rural areas to 2.75 ppbv in the urban areas where the traffic was determined to be a dominant source of BTEX emissions. Our study showed that concentration of benzene, as strictly regulated air pollutant by EU Directive 2008/50/EC, did not exceed the limit of 5 ppbv in the region in the vicinity of the crude oil refinery during the investigated period. No significant change in air quality in the vicinity of the oil refinery was discovered, however, an impact of the industry on the background air quality was detected. The T/B ratio (0.50-0.81) that was much lower than 2.0, identified other sources of pollution than traffic.     

Changes in the sorption and rate of 17β-estradiol biodegradation by dissolved organic matter collected from different water sources

The potential biodegradation and subsequent transformation of 17β-estradiol (E2) to estrone (E1) were examined in the presence of various dissolved organic matter (DOM) isolated from effluent, river and lake waters. In addition, estrogenicity was estimated in association with the removal of E2 via its sorption onto DOM and biodegradation. The more biodegradable lake-derived DOM promoted more extensive transformation of E2 into E1 than the effluent organic matter through a biodegradation process. Overall, under all conditions, biodegradation dominated the removal of E2 in water. The increased dissolved organic carbon (DOC) concentrations in river and lake-derived DOM (e.g. 6.5 mg C L(-1)) reduced the removal of E2 by decreasing its biodegradation due to the moderate sorption of E2 onto DOM. The effluent organic matter showed greater removal of E2 via biodegradation, as well as significantly high sorption. This was associated with a large amount of hydrophobic fulvic acid (FA)- and humic acid (HA)-like organic components, as shown by the small increase in the specific UV absorbance at 254 nm (SUVA(254)). An increase in the DOC concentration reduced the removal of E2, resulting in high estrogenicity. The present study suggests that both organic composition and DOC concentration influenced the removal of E2 and, therefore, should be fully considered when assessing estrogenicity and its impacts on the aquatic environment.     

MTBE (methyl tertiary-butyl ether) in groundwaters: monitoring results from Germany

In Germany information on the occurrence of MTBE in groundwaters is scarce. In order to assess the German situation, in 1999 a monitoring programme on MTBE in groundwater was set up. Within this survey 170 wells were examined, which are used as groundwater monitoring points or which are foreseen for drinking water extraction in emergency cases or for irrigation purposes. In rural areas MTBE was found only in 9% of all samples in concentrations above the limit of determination (LOD) of 0.05 microg L(-1). In urban areas MTBE was detected in 49% of all wells under investigation and the median concentration was calculated to 0.17 microg L(-1). In one case a maximum MTBE concentration of almost 700 microg L(-1) was detected. As a first result of this survey one can conclude, that MTBE is regularly present in German groundwaters under urban areas. Although investigations about the occurrence of MTBE in German groundwaters have to be extended in future, this first snapshot can lead to the assumption, that MTBE concentrations due to diffuse sources are lower than the ones found in the USA. Nevertheless, e.g. accidental spills can lead to elevated MTBE concentrations.     

Mercury in rivers in NW England: from rural headwaters to the heartlands of the historic industrial base

Total mercury (T-Hg) concentrations in rivers are described across a rural to urban/industrial and agricultural landscape gradient in NW England. T-Hg ranges between 0.2 and 230 ng L(-1). The regional median was 3.6 ng L(-1) with individual river medians ranging between 1.9 and 8.3 ng L(-1). Median T-Hg concentrations were sometimes moderately higher for the lowland areas and at higher flows. Our estimates suggest that the Ribble estuary receives 9.2 kg y(-1) and the Wyre estuary 0.7 kg y(-1). In order to examine regional inputs from urban/industrial components, regression analysis was undertaken by comparing three types of hydrochemical signature: suspended sediments (SS), which provide a measure of the particulate component, dissolved organic carbon (DOC) that provides an indication of humic/fulvic acids that are part of the organic colloids and strong chelating agents, and boron a marker of sewage effluents and population density. The results show high positive relationships of T-Hg with both SS and DOC, but no relationship with the urban/industrial signal. The regression analysis with T-Hg indicated on average a gradient of 0.33 ng mg(-1) for DOC and 0.2 ng mg(-1) for SS. They indicate the primary importance of a diffuse source of T-Hg. For the upland areas and cleaner river systems, the linkages between T-Hg and DOC were particularly strong, while for the lowland areas, the linkage with SS proved stronger. Analysis of a latter subset of data that partition the SS into organic and inorganic fractions indicated that the T-Hg was primarily linked with the organic fraction. Indeed, multiple regression of T-Hg with DOC and POM reveals gradients similar to other parts of the World.     

Simplifying and improving the extraction of nitrate from freshwater for stable isotope analyses

Determining the isotopic composition of nitrate (NO(3)(-)) in water can prove useful to identify NO(3)(-) sources and to understand its dynamics in aquatic systems. Among the procedures available, the 'ion-exchange resin method' involves extracting NO(3)(-) from freshwater and converting it into solid silver nitrate (AgNO(3)), which is then analysed for (15)N/(14)N and (18)O/(16)O ratios. This study describes a simplified methodology where water was not pre-treated to remove dissolved organic carbon (DOC) or barium cations (added to precipitate O-bearing contaminants), which suited samples with high NO(3)(-) (≥ 00 μM or 25 mg L(-1) NO(3)(-)) and low DOC (typically < 17 μM of C or 5 mg L(-1) C) levels. % N analysis revealed that a few AgNO(3) samples were of low purity (compared with expected % N of 8.2), highlighting the necessity to introduce quality control/quality assurance procedures for silver nitrate prepared from field water samples. Recommendations are then made to monitor % N together with % O (expected at 28.6, i.e. 3.5 fold % N) in AgNO(3) in order to better assess the type and gravity of the contamination as well as to identify potentially unreliable data.     

The distribution and composition of hydrocarbons in sediments from the Fladen Ground, North Sea, an area of oil production

The distribution and composition of hydrocarbons in sediment from the Fladen Ground oilfield in the northern North Sea have been investigated. The total PAH concentrations (2- to 6-ring parent and alkylated PAHs, including the 16 US EPA PAHs) in sediments were relatively low (<100 microg kg(-1) dry weight). The PAH, the Forties crude and diesel oil equivalent concentrations were generally higher in sediment of fine grain size and higher organic carbon concentration. PAH distributions and concentration ratios indicated a predominantly pyrolytic input, being dominated by the heavier, more persistent, 5- and 6-ring compounds, and with a high proportion of parent PAHs. The n-alkane profiles of a number of the sediments contained small, high boiling point, UCMs, indicative of weathered oil arising from a limited petrogenic input. The geochemical biomarker profiles of the sediments that contained UCMs showed a small bisnorhopane peak and a high proportion of norhopane relative to hopane, indicating that there was contamination from both Middle Eastern and North Sea oils. Therefore contamination was not directly as a result of oil exploration activity in the area. The most likely source of petrogenic contamination was from general shipping activity.     

Source apportionment in oil spill remediation

A pipe rupture during unloading led to a spillage of 350-700 tonnes of Ca?o Limon, a light sweet crude oil, into San Vicente Bay in 2007. Initial clean-up methods removed the majority of the oil from the sandy beaches although some oil remained on the rocky shores. It was necessary for the responsible party to clean the spilled oil even though at this location there were already crude oil hydrocarbons from previous industrial activity. A biosolvent based on vegetable oil derivatives was used to solubilise the remaining oil and a statistical approach to source apportionment was used to determine the efficacy of the cleaning. Sediment and contaminated rock samples were taken prior to cleaning and again at the same locations two days after application of the biosolvent. The oil was extracted using a modified USEPA Method 3550B. The alkanes were quantified together with oil biomarkers on a GC-MS. The contribution that Ca?o Limon made to the total oil hydrocarbons was calculated from a Partial Least Squares (PLS) analysis using Ca?o Limon crude oil as the source. By the time the biosolvent was applied, there had already been some attenuation of the oil with all alkanes 相似文献   

An Assessment of the Effects of Crude Oil Pollution on Soil Properties, Germination and Growth of Maize (Zea Mays) using Two Crude Types – Forcados Light and Escravos Light

The effect of crude oil pollution on soil properties, germination and height of maize (Zea mays) was investigated under natural environment in three separate pot experiments. Two crude oil types--Forcados light and Escravos light were used. In Experiment 1, the effect of crude oil application on germination using high pollution levels of 5, 15, 25 and 40 mL kg(-1) of soil was assessed. In Experiment 2, the effect of crude oil application on maize plant height using the same pollution levels was assessed. The last experiment (Experiment 3) was used to test for the effects of crude oil application on maize plant height using lower levels of pollution (1.0, 1.5, 2.0 and 2.5 mL kg(-1) of soil). Soil samples were collected before, during and after the experiment and analyzed for some physical and chemical properties. Results obtained showed variation in chemical properties of soil. % organic matter increased from 1.34 to 2.62% in polluted soils. Available P decreased from 15.00 ppm in control to between 7.34 and 5.42 in soils polluted with 'high' levels of crude oil. Statistical analysis of height data showed that crude oil inhibited the growth of maize at high pollution levels. High levels of pollution also inhibited germination and for Escravos light there was no germination at 40 mL kg(-1) soil level of crude oil pollution.     

Transfer of CO2, N2O and CH4 to butyl rubber (polyisobutylene) septa during storage

Greenhouse gases are more sampled than ever because of environmental interests. Gas samples are often inserted into vials with gas tight butyl rubber septa before concentration analysis. Little is known on the global transfer property of butyl rubber septa for CO2, N2O and CH4. Sorption kinetics were measured by injecting CO2, N2O or CH4 into glass vials with either one of four butyl rubber septa types and stored during 90 days. CO2 and N2O concentrations decreased during storage depending upon septa type and initial concentration, with the highest linear rate being 0.023 for CO2 and 0.0015 mg L(-3) day(-1) for N2O. When a low concentration was injected, CH4 concentration changes over time were small and did not differ between septa types. Sorption isotherms were measured using nine concentrations and stored during 45 days. CO2 sorption isotherms ranged from 0 to 3.7 x 10(-3) m(3) m(-2) and N2O from 0.3 to 1.4 x 10(-3) m(3) m(-2). Examples of errors associated with the use of these butyl rubber septa are given.     

Surfactant dissolution and mobilization of LNAPL contaminants in aquifers

Improper disposal, accidental spills and leaks of non-aqueousphase liquids (NAPL) such as gasoline, fuel oil and creosote result in long-term persistent sources of groundwater pollution.Column and 2-D tanks experiments were conducted to evaluate the use of surfactant-enhanced recovery of light non-aqueous phase liquids (LNAPL) in groundwater aquifers. These experiments focused on the use of surfactants to promote dissolution and mobilization in addition to evaluating the increase of aqueous phase permeability as residual NAPL is recovered. Further experiments are presented that show the innovative use of surfactants during primary pumping to recover free product canpotentially increase the amount of free product recovered, canpotentially reduce the amount of residual NAPL remaining afterprimary pumping and performs better than the use of surfactantsto mobilize trapped residual NAPL.     

Evaluating the Efficiency of Coagulation in the Removal of Dissolved Organic Carbon from Reservoir Water using Fluorescence and Ultraviolet Photometry

The present study used ultraviolet absorption (UVa) and the florescence intensity (FI) to evaluate the coagulation efficiency for removing dissolved organic carbon (DOC) in the raw water from Min-Ter, Li-Yu-Ten and Yun-Ho-Shen reservoirs in Taiwan. The results indicated that the ratio of DOC removal rate and FI removal rate was maintained at about 1 at various coagulant dosages. However, the ratio of DOC removal rate and UVa removal rate decreased as the coagulant dosage increased. In addition, after coagulation, the use of florescence intensity instead of total organic carbon (TOC) is better than UVa for measuring the DOC removal rate of the raw waters gathered in different months from the three reservoirs. Furthermore, a good linear relationship between florescence intensity and DOC removal rate was observed, and the DOC/FI ratio of raw water from each reservoir can be used to predict the DOC residual concentration after enhanced coagulation. This result shows that fluorescence analysis can be used for on-line and continuous monitoring the effectiveness of organic matter removal in water treatment.     

CDOM fluorescence as a proxy of DOC concentration in natural waters: a comparison of four contrasting tropical systems

Chromophoric dissolved organic matter (CDOM) fluorescence or absorption is often proposed as a rapid alternative to chemical methods for the estimation of bulk dissolved organic carbon (DOC) concentration in natural waters. However, the robustness of this method across a wide range of systems remains to be shown. We measured CDOM fluorescence and DOC concentration in four tropical freshwater and coastal environments (estuary and coastal, tropical shallow lakes, water from the freshwater lens of two small islands, and soil leachates). We found that although this method can provide an estimation of DOC concentration in sites with low variability in DOC and CDOM sources in systems where the variability of DOC and CDOM sources are high, this method should not be used as it will lead to errors in the estimation of the bulk DOC concentration.     

Use of Water Clarity to Monitor the Effects of Climate Change and other Stressors on Oligotrophic Lakes

We present evidence from studies oflakes in Killarney Park, Ontario, Canada that waterclarity is a key variable for monitoring theeffects of climate change, high UV exposure andacidification. In small oligotrophic lakes, thesestressors affect water clarity primarily byaltering the concentration of DOC in lake water. Clear lakes (<2 mg L^-1 DOC) proved to be highlysensitive indicators of stressors, exhibiting largethermal and optical responses to small changes inDOC. Extremely clear (<0.5 mg L^-1 DOC) acidic lakesshowed the effects of climate change and solarbleaching in recent decades. These lakes becamemuch clearer even though they were slowlyrecovering from acidification.     

Precipitation composition and wet deposition temporal pattern in Central Serbia for the period from 1998 to 2004

Bulk samples collected on a daily basis at three principal meteorological stations in central Serbia were analyzed on chloride (Cl(-)), nitrate [Formula: see text], sulfate [Formula: see text], sodium (Na(+)), ammonium [Formula: see text], potassium (K(+)), calcium (Ca(2+)), and magnesium (Mg(2+)) in addition to precipitation amount, pH and conductivity measurements over the period 1998-2004. The data were subjected to variety of analyses (linear regression, principal component analysis, time series analysis) to characterize precipitation chemistry in the study area. The most abundant ion was [Formula: see text] with annual volume weighted mean concentration of 242 microeq L(-1). Neutralization of precipitation acidity occurs both as a result of the dissolution of alkaline compounds containing Ca(2+), Mg(2+), and K(+) as well as the absorption of ammonia. The ratio of [Formula: see text] was above 5, which indicated that the combustion process of low-grade domestic lignite for electricity generation from coal-fired thermal power plants was the main source of pollution in the investigated area. A considerable mean annual bulk wet deposition of SO(4)-S determined by precipitation amount and concentrations of sulfate in the precipitation was calculated to be 12-35 kg ha(-1).     

Assessment of cyclodextrin-enhanced extraction of crude oil from contaminated porous media

The purpose of this study was to evaluate the effects of cyclodextrin (CD) on the extraction of Macondo well oil from contaminated porous media over a range of hydroxypropyl-β-CD (HPβCD) concentrations. To our knowledge, this is the first dataset on this type of CD yet assembled for an actual crude oil. The results showed that HPβCD can significantly increase oil extraction efficiency, demonstrated by increasing concentrations of all tested normal alkanes (nC(15)-nC(35)) and polyaromatic hydrocarbons (PAHs) in the aqueous phase with increasing CD concentration. A linear relationship between the extraction enhancement effect and CD concentration were verified experimentally and high correlation coefficients for total PAHs (R(2) = 0.82) and alkanes (R(2) = 0.99) were determined. For a 20% CD solution, 3.13 wt% of alkanes and 32.12 wt% of total PAHs were extracted to the aqueous phase, which was significantly more than what was extracted with water only (0.04% and 0.21% for alkanes and PAHs, respectively). This result shows that the remediation of oil contaminated media can be significantly enhanced through the use of HPβCD solutions in flushing or pump and treat operations to remove sorbed oil. The CD extraction enhancement effect decreases with increasing n-alkane chain length for the carbon number range tested. CD significantly enhanced PAH extraction from sand and the enhancement effect increased in the order of parent compounds < C-1 substituted < C-2 substituted < C-3 substituted for most PAHs tested. This study provides important information to assess the feasibility of using CD as a near-shore agent to enhance the cleanup of oil contaminated porous media.