The use of surface-enhanced Raman scattering (SERS) for detection of PAHs in the Gulf of Gdańsk (Baltic Sea)

A field operable surface enhanced Raman scattering (SERS) sensor system was applied for the first time under real conditions for the detection of polycyclic aromatic hydrocarbons (PAHs) as markers for petroleum hydrocarbons in the Gulf of Gdańsk (Baltic Sea). At six stations, seawater samples were taken, and the sensor system was applied in situ simultaneously. These measurements were compared to the results of conventional GC/MS laboratory analysis of the PAH concentrations in the seawater samples. For a PAH concentration above 150 ng(12PAH)l(-1), there was agreement between the SERS sensor and the GC/MS determinations. A standard addition experiment yielded a PAH concentration of 900 ng l(-1) at the Gdańsk Harbor, which was of the same order as the GC/MS determinations of 12PAHs (200 ng(12PAH)l(-1)). The high SERS detection limit for seawater samples is explained by the competition for PAHs between the sensor membrane and particulate matter surfaces. Thus, the SERS sensor can be applied, e.g., as a non-quantitative alarm sensor for relatively high PAH concentrations in heavily polluted waters. The spectral unmixing procedure applied for Gdańsk Harbor water confirmed the presence of phenanthrene at the highest concentration ([Phe]=140 ngl(-1)) and of Chr (2.7 ng l(-1)), but it did not detect the other PAHs present in the Gdańsk Harbor water, as determined by GC/MS. When compared to the past literature and databases, the SERS spectra indicated the presence of a mixture of molecules consisting of carotenoids, n-alkanes, amines or fatty acids, and benzimidazoles at the coastal station ZN2. The spectra in the offshore direction indicated carboxylic acids. Interpretation of the farthest offshore in situ SERS measurements is difficult, principally due to the limited availability of reference spectra. The detection of the lower PAH concentrations commonly found in Baltic coastal water needs further research and development to obtain better sensitivity of the SERS sensor. However, the high analytical specificity of the SERS sensor also allows the detection of other chemical species that require the development of a SERS/Raman library for specific in situ spectral interpretation.     

An assessment of the pollutant status of surficial sediment in Cork Harbour in the South East of Ireland with particular reference to polycyclic aromatic hydrocarbons

Surface sediment from three polluted sites within Cork Harbour, Ireland, and from a relatively clean reference site were collected and analysed for polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), brominated flame retardants (BFRs), organotins (OTs), and heavy metals. PAHs were determined to be the most abundant class of contaminant. Concentrations of the sum (Sigma) of the 21 PAHs measured from the Harbour sites (2877.70 ng g(-1), 1000.7 ng g(-1) and 924.40 ng g(-1) dry weight respectively) were significantly higher than that of the sediment from the reference site (528.30 ng g(-1) dry weight). An inner harbour site, Douglas being the more contaminated of the three harbour sites. A similar pattern was observed with the other contaminants however, these compounds, with the exception of the heavy metals, all tended to be detected at concentrations on or below detection limits.     

Distribution and sources of polynuclear aromatic hydrocarbons in Mangrove surficial sediments of Deep Bay, China

Twelve sediment samples collected from three transects of mangrove swamp of Deep Bay, Shenzhen, China, were determined for polynuclear aromatic hydrocarbons (PAHs). The total PAHs concentrations ranged from 237 to 726 ng g(-1) dry weight, and showed strong correlation with total organic carbon (TOC), clay content and Pb concentrations. The highest PAHs concentrations were found in the samples from mangrove sediments. Overall, PAHs in Deep Bay sediment were lower than those in other developed areas. The biological effect due to PAHs alone in Deep Bay is expected to be low, based on the comparisons of individual and total PAHs concentrations determined in the sediment with those in USEPA sediment quality guidelines. Four and five-ring compounds dominated the PAHs composition pattern profiles. Principal component analysis (PCA) was applied to further investigate the source of PAHs. The PAH sources of Deep Bay mangrove swamp were suggested to be primarily combustion of fossil fuel, especially leaded-gasoline exhaust.     

Polycyclic aromatic hydrocarbons loads into the Mediterranean Sea: estimate of Sarno River inputs

The polycyclic aromatic hydrocarbons (PAHs) pollution in the Sarno River and its environmental impact on the Gulf of Naples (Tyrrhenian Sea, Central Mediterranean Sea) were estimated. The 16 PAHs identified by the USEPA as priority pollutants and perylene were determined in the water dissolved phase (DP), suspended particulate matter (SPM) and sediments. Total PAHs concentrations ranged from 23.1 to 2670.4 ng L(-1) in water (sum of DP and SPM) and from 5.3 to 678.6 ng g(-1) in sediment samples. Source analysis revealed that PAHs mainly came from combustion process. Contaminant discharges of PAHs into the sea were calculated in about 8530 gd(-1) showing that this river should account as one of the main contribution sources of PAHs to the Tyrrhenian Sea.     

Dynamic behaviour of polycyclic aromatic hydrocarbons in Brighton marina, UK

The distribution of polycyclic aromatic hydrocarbons (PAHs) between various phases is fundamental in the control of their movement and impact in the marine environment. In this study samples of water and sediments were regularly collected from Brighton marina, UK, to quantify the intensity, spatial and temporal variations of PAH contamination. The results show clearly that PAH behaviour in marine systems is highly complex, and controlled by the interplay of PAH sources, compound physicochemical properties, water and sediment movement, and field conditions. Levels of total PAHs (16 compounds) in the dissolved phase were found to vary between <2 and 11,400 ng/l, with higher values observed in the winter months. Total PAH concentration in sediment samples varied between 24 and 4710 ng/g dry weight. PAHs in water were dominated by low molecular mass compounds (2-ring), while PAHs in sediments were mainly derived from 2-4 ring compounds. In addition, dissolved concentrations were increased during sediment dredging and after a period of severe rainfall. PAHs in Brighton marina are likely to be from both pyrolytic and petrogenic sources; as a result, field-derived distribution coefficients for individual PAHs between sediment and water tend to follow the equilibrium partition models, although slight exceedance is apparent. The extended partition model incorporating soot carbon has achieved limited success in better predicting PAH behaviour.     

巢湖表层沉积物中多环芳烃分布特征及来源

于2010年,采用野外采样调查、色谱分析与统计比较的方法,研究巢湖表层沉积物中27个采样点中多环芳烃(PAHs)分布特征及污染来源.结果表明:巢湖表层沉积物中检测出的14种优控PAHs总浓度为116.0~2832.2 ng/g(DW),平均值为898.9±791.0 ng/g(DW).多环芳烃组成主要以5~6环PAHs为主,占总量的32%~58%.沉积物中总有机碳含量与PAHs总量呈现良好相关性.利用蒽/(蒽+菲)与苯并[a]蒽/(苯并[a]蒽+屈)比值法对PAHs来源进行解析得出,巢湖表层沉积物中PAHs主要来源为燃烧源.与国内其它水体PAHs含量对比表明,巢湖沉积物中PAHs污染处于中等水平.生态风险评估得出南淝河表层沉积物中PAHs存在生态风险,其它采样点表层沉积物中PAHs生态风险均较低.     

Study on the fate of petroleum-derived polycyclic aromatic hydrocarbons (PAHs) and the effect of chemical dispersant using an enclosed ecosystem,mesocosm

Polycyclic Aromatic Hydrocarbons (PAHs) are one of the components found in oil and are of interest because some are toxic. We studied the environmental fate of PAHs and the effects of chemical dispersants using experimental 500 l mesocosm tanks that mimic natural ecosystems. The tanks were filled with seawater spiked with the water-soluble fraction of heavy residual oil. Water samples and settling particles in the tanks were collected periodically and 38 PAH compounds were analyzed by gas chromatography-mass spectrometry (GC-MS). Low molecular weight (LMW) PAHs with less than three benzene rings disappeared rapidly, mostly within 2 days. On the other hand, high molecular weight (HMW) PAHs with more than four benzene rings remained in the water column for a longer time, up to 9 days. Also, significant portions (10-94%) of HMW PAHs settled to the bottom and were caught in the sediment trap. The addition of chemical dispersant accelerated dissolution and biodegradation of PAHs, especially HMW PAHs. The dispersant amplified the amounts of PAHs found in the water column. The amplification was the greater for the more hydrophobic PAHs, with an enrichment factor of up to six times. The increased PAHs resulting from dispersant use overwhelmed the normal degradation and, as a result, higher concentrations of PAHs were observed in water column throughout the experimental period. We conclude that the addition of the dispersant could increase the concentration of water column PAHs and thus increase the exposure and potential toxicity for organisms in the natural environment. By making more hydrocarbon material available to the water column, the application of dispersant reduced the settling of PAHs. For the tank with dispersant, only 6% of chrysene initially introduced was detected in the sediment trap whereas 70% was found in the trap in the tank without dispersant.     

Perylene dominates the organic contaminant profile in the Berau delta, East Kalimantan, Indonesia

The geographical distributions of polyaromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), hexachlorobenzene, and 1,1-dichloro-2,2-bis(4-chlorophenyl)ethene (4,4'-DDE) were studied in the Berau delta (East Kalimantan, Indonesia), using sediment sampling and passive water sampling with semipermeable membrane devices. High concentrations of perylene were observed in sediments (54-580 ng g(-1) dry weight), and water (1-680 pg L(-1)). Perylene accounted for about 60% of the total concentrations of PAHs in the sediment. The relative abundance of the other PAHs was indicative of petrogenic sources. Concentrations of PCBs, hexachlorobenzene, and 4,4'-DDE in sediments were below or close to the detection limit (～ 0.02 ng g(-1)). The analysis of a sediment core revealed no appreciable changes in the concentration of target compounds over the past three decades. We show that sediment sampling and passive water sampling are complementary techniques, and propose to bring the results of both methods to the same concentration scale, using locally derived sediment-water partition coefficients.     

Sedimentary record of polycyclic aromatic hydrocarbons in a sediment core from the Pearl River Estuary, South China

Owing to the hydrodynamic and sedimentation conditions, the western shoal of the Pearl River Estuary (PRE) is known to be an important sink of terrestrial substances including particle-associated pollutants from the Pearl River Delta (PRD) region. In this study, we report the sedimentary record of polycyclic aromatic hydrocarbons (PAHs) during the 20(th) century in a sediment core from the western shoal of the PRE. The summation PAH concentration ranged from 59 ng g(-1) to 330 ng g(-1) in the core with two distinct peaks. An initial increase of summation PAH concentration was found around the 1860s. The amounts of PAHs remained relatively constant for roughly 100 years, followed by the first peak in the 1950s. Then, there was a decrease in PAH concentration and flux in the 1960s and 1970s. A sharp increase of PAH concentration was observed in the early 1980s with a maximum concentration in the 1990s. The PAH diagnostic ratios indicated that the PAHs in the sediment core were mainly of pyrolytic origin, and that atmospheric deposition and land runoff may serve as the important pathways for PAHs input to the sediment. The Gross Domestic Product (GDP) was used as an index of socioeconomic development in the PRD region, which was correlated positively with the changes of PAH concentration and flux in the sediment core. The rapid increase in vehicle numbers and energy consumption in the region in the last two decades may have contributed to the rapid PAH increase since the early 1980s. The results clearly elucidated the impact of regional economic development on the estuarine environment.     

河北西大洋水库沉积物中多环芳烃的分布、来源及生态风险评价

分析了河北西大洋水库沉积物中16种多环芳烃的含量及分布状况,并对其来源和生态风险进行了分析和评估.结果表明,表层沉积物多环芳烃总含量范围在422.36 - 1052.90 ng/g之间,且由库区上游到坝前逐渐升高.水库剖面沉积物中多环芳烃总含量在388.81 - 1205.56 ng,/g之间,自底层20 cm到表层多...     

小白洋淀水-沉积物系统多环芳烃的分布、来源与生态风险

以端村小白洋淀为研究对象,利用GC-MS测定了6个样点水、悬浮物和沉积物中15种优控多环芳烃(PAHs)的含量,分析了其组成与来源特征,探讨了不同多环芳烃单体的生态风险,结果表明:(1)15种优控多环芳烃的总含量(PAH15),水相为40.1-74.0ng/L,算术均值51.0ng/L;悬浮物为2438.0-5927.0ng/g,算术均值4528ng/g;沉积物为466.9-1366.4ng/g,算术均值为755.6ng/g;与国内外有关研究相比,污染较轻,(2)三相中均以2、3环PAHs为主,其比例均高于80%;并且,从水相、悬浮物相到沉积物相,2环PAHs依次降低,3环、4环依次升高,高环检出率和含量也依次升高,(3)沉积物中多环芳烃的来源以生物质燃料(秸秆、薪材)和煤的燃烧为主,以液体化石燃料(汽油、柴油和原油)的燃烧为辅,(4)沉积物中的芴(FLO)、菲(PHE)含量在潜在生态风险效应区间低值(ERL)与中值(ERM)之间,其生态风险几率介于10%-50%之间;其他PAHs单体的含量均低于ERL,其生态风险几率均低于10%.     

Polycyclic aromatic hydrocarbons in water and sediment of the Baltic Sea

Between 1992 and 1994, the distribution of 15 polycyclic aromatic hydrocarbons (PAHs) was investigated in seawater and surface sediments of the Baltic Sea. The analysis of PAHs in seawater is very difficult due to the low concentration. High separation capability is required. A method for analysing very low concentrations of PAHs is presented. The method is based on the high-performance liquid chromatography (HPLC) with fluorescence detection. The concentrations of PAHs in seawater are discussed in relation to water depth. A seasonal variation of PAHs in seawater was observed, with lowest concentrations occurring in summer and generally higher concentrations occurring in November. According to the regional distribution, elevated concentrations of PAHs were found in coastal regions of the Baltic Sea. The regional distribution of PAHs in surface sediments of the Belt Sea and the Arkona Basin were also investigated. The relationship between the content of PAHs and the percentage of total organic carbon in sediments is discussed.     

The partitioning of Triclosan between aqueous and particulate bound phases in the Hudson River Estuary

The distribution of Triclosan within the Hudson River Estuary can be explained by a balance among the overall effluent inputs from municipal sewage treatment facilities, dilution of Triclosan concentrations in the water column with freshwater and seawater inputs, removal of Triclosan from the water column by adsorption to particles, and loss to photodegradation. This study shows that an average water column concentration of 3 ± 2 ng/l (in the lower Hudson River Estuary) is consistent with an estimate for dilution of average wastewater concentrations with seawater and calculated rates of adsorption of Triclosan to particles. An average Triclosan sediment concentration of 26 ± 11 ng/g would be in equilibrium with the overlying water column if Triclosan has a particle-to-water partitioning coefficient of k_d  10⁴, consistent with laboratory estimates.     

Monitoring of organic pollutants in coastal waters of the Gulf of Gdańsk, Southern Baltic

This paper presents an overview of changes in organic pollution of coastal waters of the Gulf of Gdańsk (Baltic Sea). Toxic pollutants including volatile organic compounds (VOC), volatile organohalogen compounds (VOX), chlorophenols, phenoxyacids, polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) were determined in seawater from the Gulf of Gdańsk coastal waters in the period 1996-2001. In the case of the Gulf of Gdańsk, non-conservative behaviour of VOC was observed due to random temporal and spatial of inputs along the Vistula estuary and to the dilution of VOC-enriched river water with seawater. The concentrations of VOX in seawater decreased throughout the period and the concentrations of VOX were in the range of few ng dm(-3) up to 250 ng dm(-3), similar to estuaries elsewhere. The average concentrations of chlorophenols and phenoxyacids were between 0.1 and 6.0 and 0.05 and 2.2 microg dm(-3), respectively. However, remarkably high concentrations of 2,4-dichlorophenol (6 microg dm(-3)) were obtained in samples collected from the Vistula River. Generally concentrations of PCBs did not exceed few ng dm(-3) with the exception of 1999, when all samples exhibited elevated concentrations of PCBs. In addition, higher concentrations of PCBs in the open sea compared to river waters suggested localised inputs. Due to the ability of most organic pollutants to bioaccumulate and biomagnify, especially the persistent organic pollutants, continued monitoring is of crucial importance for the health of marine life in the Gulf of Gdańsk.     

Application of an impact plate – Bedload transport measuring system for high-speed flows

To achieve the sustainable use of dams, the development of methods for sediment management in reservoirs is required. One such method includes the use of Sediment Bypass Tunnels (SBTs) to divert sediment around a dam, thereby preventing sedimentation in the reservoir. However, SBTs are prone to severe invert abrasion caused by the high sediment flux. Therefore, it is necessary to establish a measurement system of the sediment transport rate in these tunnels. One system to measure sediment transport in rivers is the Swiss plate geophone, which can register plate vibrations caused by particle impact. In Japan, the Japanese pipe microphone is used, and sediment transport is measured based on the sound emitted by the particle impact. In this study an attempt was made to optimize the advantages of both systems by fixing a microphone and an acceleration sensor to a steel plate. The results of calibration experiments with this new system are presented and compared with the existing methods. It was found that the acceleration sensor can detect sediment particles larger than 2 mm in diameter. Moreover, a new parameter, referred to as the detection rate, was introduced to describe the correlation between the actual amount of sediment and the registered output. Finally, two parameters - the saturation rate and hit rate - are introduced and exhibit strong correlation with the detection rate.     

Chlorinated pesticides and PCBs in the sea-surface microlayer and seawater samples of Singapore

Sea-surface microlayer (SML) and seawater samples collected from Singapore's coastal marine environment were analyzed for selected chlorinated pesticides and polychlorinated biphenyls (PCBs). The SML is a potential site of enrichment of persistent organic pollutants (POPs) compared to the underlying water column. The concentration ranges of SigmaHCH, SigmaDDT and SigmaPCB in subsurface (1 m depth) seawater were 0.4-27.2 ng/l (mean 4.0 ng/l), 0.01-0.6 ng/l (mean 0.1 ng/l) and 0.05-1.8 ng/l (mean 0.5 ng/l) respectively. In the SML, the concentration ranges of SigmaHCH, SigmaDDT and SigmaPCB were 0.6-64.6 ng/l (mean 9.9 ng/l), 0.01-0.7 ng/l (mean 0.2 ng/l) and 0.07-12.4 ng/l (mean 1.3 ng/l) respectively. High spatial and temporal distribution was observed for all POPs measured. However, overall levels measured in the SML were lower than levels reported in the literature for SML samples from temperate coastal regions-possibly due to loss of semi-volatile compounds in the tropical climate of Singapore. Atmospheric wet deposition during the monsoon season may be an important source of POPs to the SML. This study provides the first scientific data on POP concentrations and enrichment factors in the SML for Southeast Asia.     

Caffeine in Boston Harbor seawater

Caffeine has been detected in Boston Harbor seawater with concentrations ranging from 140 to 1600 ng l(-1), and in Massachusetts Bay seawater at concentrations from 5.2 to 71 ng l(-1). Sources of caffeine appear to be anthropogenic with higher concentrations in the seawater of Boston's inner harbor and in freshwater sources to the harbor. Charles River water and Deer Island sewage treatment plant effluent, the two major sources of freshwater to the harbor, contained 370 and 6700 ng l(-1) of caffeine, respectively, in 1998. Sewage influent and effluent concentrations appear to be consistent with consumption estimates of caffeinated beverages for the Boston area and total organic carbon removal targets for treated sewage. Caffeine was inversely correlated to salinity in a transect from the mouth of Boston Harbor to Stellwagen Basin, indicating it may be a useful chemical tracer of anthropogenic inputs to marine systems.     

Sources and geochemical constraints of polycyclic aromatic hydrocarbons (PAHs) in sediments and mussels of two Northern Irish Sea-loughs.

Polycyclic aromatic hydrocarbons (PAHs) were sampled from 30 sediment and 8 mussel (Mytilus edulis) stations in two Northern Irish Sea-toughs. Analysis was performed by gas chromatography coupled to mass spectrometry (GC-MS). Sedimentary organic carbon, % silt/clay and mean grain size were analysed in order to assess the role of geochemistry on PAH distribution. With the exception of two sites in Larne Lough representing localized regions of high contamination, sum(PAHs) in sediments ranged between 83 and 2300 ng g(-1). Regression analysis indicated that particle size and organic C were dominant factors in controlling the distribution of PAHs throughout the sediments. Sources of PAHs in both sea-loughs were dominated by pyrogenic inputs suggesting that diffuse sources such as atmospheric deposition may be a major source to both water bodies. The sum of PAHs in mussels ranged between 95 and 184 ng g(-1). Variations in concentrations may be explained by differences in the condition between mussel populations. Mussels in both sea-loughs exhibit similar metabolic activities towards the PAH compounds which were predominantly bioaccumulated from sediments.     

PAH-profiles in sediment cores from the Baltic Sea

To document the historical input the PAH-profiles of sediment cores in two different basins of the Baltic Sea, the Gotland Basin (GB) and Arkona Basin (AB), were analysed by means of GC-MS. 35 PAHs were quantified in all samples, and additionally, several marker PAHs, like Cyclopenta[cd]phenanthrene (CCP) for combustion processes and retene for terrigenous input, were quantified in selected samples. The preindustrial sediments (older than 200-250 years) in the GB core illustrate concentrations <100 ng PAH15 g(-1) d.w. Calculated PAH-ratios indicated combustion processes as the main sources for both basins. The Perylene concentrations within the sediment cores decrease with increasing depth, along with an increase in relative percentage, indicating slow diagenetic processes. The preservation and enrichment of the introduced PAHs was more pronounced in the GB core.     

Distribution and origins of polycyclic aromatic hydrocarbons (PAHs) in riverine, estuarine, and marine sediments in Thailand

To assess the status of polycyclic aromatic hydrocarbon (PAH) contamination in coastal and riverine environments in Thailand, we collected 42 surface sediment samples from canals, a river, an estuary, and coastal areas in Thailand in 2003 and analyzed them for PAHs with 3-7 benzene rings by gas chromatography-mass spectrometry (GC-MS). The total concentration of PAHs ranged from 6 to 8399 ng/g dry weight. The average total PAH concentrations were 2290+/-2556 ng/g dry weight (n=8) in canals, 263+/-174 (n=11) in the river, 179+/-222 (n=9) in the estuary, and 50+/-56 (n=14) in coastal areas. Comparison of the concentration range with a worldwide survey of sedimentary PAH concentrations ranked PAH contamination in Thai sediments as low to moderate. The ratio of the sum of methylphenanthrenes to phenanthrene (MP/P ratio) allows discrimination of PAH sources between petrogenic (>2) and pyrogenic (<0.5) origins. Sediments from urban canals in Bangkok showed the highest PAH concentrations and petrogenic signatures (MP/P=1.84+/-0.98 [n=6] in canal sediments) with abundant alkylated PAHs, indicating major sources of petrogenic PAHs in the city. To identify the sources of the petrogenic inputs in Thailand, we analyzed triterpanes, biomarkers of petroleum pollution, in the sediment samples and in potential source materials. Hopane profiles were remarkably uniform throughout the nation, suggesting a diffuse single source (e.g. automobiles). Molecular profiles of hopanes and PAHs in sediments from the urban canals were similar to those in street dust, indicating that street dust is one of the major sources of petrogenic PAHs in the urban area. On the other hand, low levels of PAHs (approximately 50 ng/g) with a pyrogenic signature (MP/P ratio approximately 0.5) were widely recorded in remote areas of the coast and the Chao Phraya River. These pyrogenic PAHs may be atmospherically transported throughout the nation. Middle and lower reaches of the Chao Phraya River, the river mouth, and the upper Gulf of Thailand showed intermediate concentrations and profiles of PAHs, indicating mixtures of petrogenic and pyrogenic origins. Perylene was abundant in sediments, representing up to approximately 60% of total identified PAHs. High inputs of soil due to frequent heavy rains could contribute to the high perylene abundance in the sediments. Sedimentary PAH concentrations decreased offshore with a half distance of approximately 10 km in the upper Gulf off the mouth of the Chao Phraya River. This is probably due to active deposition of laterally transported riverborne particles.