天津城郊土壤中PAHs含量特征及来源解析

以天津市郊环城四区为研究对象,系统采集了环城四区95个表层土壤样品,利用高效液相色谱仪对16种PAHs进行分析测定,结果表明,西青、东丽、津南和北辰土壤中16种PAHs的总量范围分别为62.6～1 994.9、36.1～4 074.7、20.1～2 502.5、22.1～707.7μg/kg;平均含量分别为445.8、841.8、509.5、242.5μg/kg。四区中都以高环多环芳烃为主,西青、东丽、北辰和津南高环多环芳烃分别占多环芳烃总比例的45.4%、42.2%、38.8%和38.7%。空间分析的结果表明,靠近天津市市区样点土壤中多环芳烃的含量要明显高于远离市区土壤中多环芳烃的含量。利用环数PAHs的相对丰度和比值法对天津市郊环城四区土壤中多环芳烃的污染来源进行了解析,研究区土壤监测样点的PAHs主要来自燃烧源,少部分来自石油类来源或几种污染源的共同复合累加的作用。     

河北省近岸海域氮磷变化及其影响因素分析

根据2011—2018年河北省近岸海域海水、入海河流、降水中氮和磷的监测数据,分析了海水中氮和磷的变化趋势及其影响因素。结果表明：2011—2018年,河北省近岸海域海水中无机氮（DIN）和无机磷（DIP）的平均浓度均低于第二类海水水质标准,海域富营养化状况以贫营养和轻度富营养为主,超标（第二类海水水质标准限值）点位和中度、重富营养区域主要集中在沧州市近岸海域。河北省近岸海域海水中DIN的平均浓度在2011—2014年、2015—2017年呈现阶段性上升趋势,2018年大幅下降;DIP的平均浓度在2011—2013年无明显波动,2014年陡增后开始逐年下降;N/P在2011—2014年无明显变化,2015—2018年呈逐年上升趋势。自2016年起,入海河流中氨氮和总磷的平均浓度、降水中氨氮的平均浓度均呈逐年下降趋势。近岸海域海水、入海河流、降水中的氮和磷表现出一定的相关性和协同性,陆源污染输入总量降低是海水中氮磷浓度降低的主要原因。应警惕污染物控制力度的不同所导致的海水中生源要素结构的改变,及其引发的潜在海洋生态风险。     

一种便携式荧光测油仪在海上溢油应急监测中的适用性研究

研究了一种便携式荧光测油仪在海上溢油应急监测中的适用性,并与现行仲裁标准方法进行比较分析。研究表明:该便携式荧光测油仪测定海水中油类样品仅需100 mL水样,平均每个样品所需的前处理时间约340 s,方法检出限为0.003 mg/L,测定下限为0.012 mg/L。测定用标准物质配制的不同浓度海水样品,相对标准偏差为0.08%~0.87%,测定标准样品的相对误差为0.49%~4.50%,实际样品加标回收率为90%~107%。对标准物质配制的海水样品进行检测,与现行仲裁标准方法在0.05水平下无显著性差异。在渤海中部海上监测中,连续6 d测定不同标准样品的相对标准偏差为0.26%~0.83%。研究结果表明,该便携式荧光测油仪适用于现场对油类的定量分析和水质评价。     

Chemical Characteristics and Source Implications of Petroleum Hydrocarbon Contaminants in the Sediments near Major Drainage Outfalls along the Coastal of Laizhou Bay, Bohai Sea, China

The associated industrial and urban developments are located to a large extent along the Laizhou Bay, Bohai Sea coastal and raw sewage is often discharged into near shore waters with little treatment. To find out chemical characteristics and pollution source of the petroleum related contaminations in sediments near the major drainage outfalls located in the coastal, in this study, 10 surface sediment samples were collected during June. Sediment samples were extracted by organic solvents, separated by silica gel column chromatography and the concentrations and the profiles of n-alkane, biomarker and PAH in sediments were analyzed by gas chromatography-mass selective detector (GC-MSD). The use of several molecular markers and related indexes derived for n-alkane and PAHs has been proposed for assessing the relative contributions to the environment of hydrocarbon sources. As a result, n-alkanes reflect that the sea area of paper mill (Station ZZ08) is dominated by vascular plant. DY petroleum oil field and outer shore of the paper mill (Station ZZ02) have some degrees of petroleum related hydrocarbon contamination. Whereas the contamination of the sea area of TH River may be ascribed to different sources such as territorial non-point pollution source, domestic sewages, and stormwater runoff. Judged by their PAH ratios, the sediments near the paper mill (Station ZZ02) and the outer station of the oil field (Staion TH2) were pyrolytic. The estuary of Tiao River including the inner Station THX, TH10 and TH05 are petrogenic. The marine sediment near DY drainage outfall may have a mixture source of PAH both pyrolytic and petrogenic.     

The use of marine sponge, Haliclona tenuiramosa as bioindicator to monitor heavy metal pollution in the coasts of Gulf of Mannar, India

The results of the present research study indicate that the heavy metal accumulation in the marine sponges provide evidence as an excellent bioindicators for monitoring heavy metal pollution between near and offshore environments of Mandapam coast of "Gulf of Mannar (GoM), India". The heavy metal concentrations in sea water and accumulation in the tissues of Haliclona tenuiramosa were analyzed by ICP-MS (inductively coupled plasma-mass spectrometry). The concentrations of metals in the coastal waters of nearshore (< 0.5 km from shore) were always higher than those in the offshore waters (2-5 km away from shore). Likewise, sponges living in the nearshore accumulated greater concentrations of heavy metals (As, Cd, Co, Cu, Fe, Mn and Ni) ranging from 2 to 17 times higher concentration than the sponges located away from the shore. A positive correlation between concentration levels in water and bioaccumulation in tissues was observed. The bioaccumulation of heavy metals in sponge tissue were in order of Fe > Mn > Ni > Cu > As > Co > Cd in both the near and offshore stations. The present results justified that a more comprehensive monitoring of presence of heavy metals in H. tenuiramosa of surrounding GoM, is necessary to help a better mitigation of the problem.     

Spatial and temporal distribution of tributyltin (TBT) in seawater, sediments and bivalves from coastal areas of Korea during 2001–2005

Tributyltin (TBT) concentrations were determined in seawater, sediments and bivalve samples collected from Korean coastal areas during 2001-2005, to investigate the levels and temporal variation in TBT contamination in relation to the timing of the imposition of regulations on TBT use in Korea. TBT concentrations ranged from <5.0 to 164 ng/L in seawater, from <7.0 to 9,576 ng/g dry weight in sediments, and from <7.0 to 6,296 ng/g dry weight in bivalves. The highest concentrations of TBT were found at locations close to intensive shipping traffic and industrial complexes, and the contamination at some hot spot areas was high enough to cause harmful effects on marine organisms. TBT concentrations and their occurrence in Korean coastal waters have been decreasing annually. In particular, TBT concentrations in seawater have dramatically decreased. This result is consistent with regulations and bans on the use of TBT in Korea.     

Identification of copper sources in urban surface waters using the principal component analysis based on aquatic parameters

The goal of this work was to identify the sources of copper loads in surface urban waters using principal component analysis under the aquatic parameters data evaluation approach. Water samples from the Irai and Iguacu rivers were collected monthly during a 12-month period at two points located upstream and downstream of a metropolitan region. pH, total alkalinity, dissolved chloride, total suspended solids, dissolved organic matter, total recoverable copper, temperature, and precipitation data provided some reliable information concerning the characteristics and water quality of both rivers. Principal component analysis indicated seasonal and spatial effects on copper concentration and loads in both environments. During the rainy season, non-point sources such as urban run-off are believed to be the major source of copper in both cases. In contrast, during the lower precipitation period, the discharge of raw sewage seems to be the primary source of copper to the Iguacu River, which also exhibited higher total metal concentrations.     

In situ laser-induced fluorescence (LIF) analysis of petroleum product-contaminated soil samples

General considerations of the calibrations of in situ measurements are presented and the concept of using an "average oil" with average analysability for calibration purposes is introduced. The in situ analysis of 30 petroleum product-contaminated soil samples with laser-induced fluorescence (LIF) spectroscopy was performed. Compared to an uncontaminated laboratory reference (LR) soil, 23 soil samples exhibited significantly higher LIF signals, so that these soil samples were classified as contaminated. The repeatability and reproducibility of the in situ LIF analysis were investigated. For the calibration of the LIF data, two LR oils (a fuel oil and a crude oil) were employed. The degree of soil contamination with petroleum products ranged from the limit of detection (LOD) for LIF analysis (ca. 100 ppm), or below, to more than 10,000 ppm. The petroleum product concentrations determined with in situ LIF analysis reveal a reasonable correlation with the results of standard IR analysis after extraction of the contaminated soils.     

Determination of O3, NO2, SO2, CO and PM10 measured in Belgrade urban area

O(3), NO(2), SO(2), CO and PM(10) concentrations, simultaneously determined for the first time in Belgrade urban area in the autumnal period of 2005, are presented. The obtained results display similar behaviour of SO(2), NO(2), CO, PM(10) opposite from that of O(3). The weekend effect was also investigated showing diminution of average daily concentrations of SO(2), NO(2), PM(10) and CO for 72, 40, 37 and 42% respectively, and increase of the average daily concentration of O(3) for 56%. Influence of meteorological conditions on observed concentration levels was studied, too. The observed influence of wind speed on the O(3) nightly concentration levels was analyzed pointing to the phenomena of O(3) transport during episodic measurements. To make an identification of possible pollution sources and analyse the influence of meteorological parameters on pollution levels, air back trajectories for high level concentrations episodes were calculated and analysed. A multivariate receptor modelling (Principal Component Analysis, Cluster Analysis) has been applied to a set of data in order to determine the contribution of different sources. It was found that the main principal components, extracted from the air pollution data, were related to gasoline combustion, oil combustion and ozone transport.     

Occurrence of PAHs and PCBs in the Alna River, Oslo (Norway)

Thirty two polychlorinated biphenyl congeners (PCBs), hexachlorobenzene (HCB) and pentachlorobenzene (PeCB) were analysed in passive sampler extracts from surface water-exposed semipermeable membrane devices (SPMDs) and in bed sediment samples from a small urban watercourse, the River Alna (Oslo, Norway). Performance reference compound-corrected data from the passive samplers deployed at three sites along the river were used to track PCB contamination in the overlying water. SPMDs were able to detect an increase in dissolved PCB concentrations at the site furthest downstream that was corroborated by bed sediment concentrations. In comparison, no major increase in concentration of HCB, PeCB or PAHs could be observed. Comparison of passive sampling-based overlying water concentrations with total concentrations measured in bed sediments supports the possibility of further PCB sources upstream of the study area. Diagnostic PAH ratios (from SPMDs) and PCB congener pattern (from sediments) were used in an attempt to identify possible contaminant sources to the Alna River. Selected PAH diagnostic ratios support a multiple emission source scenario and demonstrate the complexity of identifying specific sources of these compounds to surface waters. PCB congener patterns in sediments from all three sites tend to indicate a source of highly chlorinated PCBs (of the Archlor 1260 type) and either a source of lower chlorinated PCBs or the less-likely occurrence of dechlorination in sediment. Information collected during the present screening study also confirms the Alna River as a continuous source of PCBs to the Oslofjord.     

Flow-injection analysis with fluorescence detection for the determination of trace levels of ammonium in seawater

A method using flow-injection, gas-diffusion, derivatisation and then fluorescent detection has been established for ammonium ion determination in seawater. The fluorescent derivative formed by reacting ortho-phthaldialdehyde (OPA) and sulfite with ammonia gives high sensitivity while removing potential interferences. This is required to measure the low concentrations of ammonium often seen in the open ocean. The experimental conditions (flow-rate, reagent concentrations, membrane configurations, etc.) were manipulated to improve performance. For a sample throughput of 30 samples h(-1), the limit of detection was 7 nM, the coefficient of variation was 5.7% at 800 nM, and the calibration curve was linear to at least 4 micromol L(-1). Interferences were minimised by a gaseous diffusion step. Volatile small molecular-weight amines as interferents were discriminated against by this method. They neither passed through the membrane as efficiently as ammonia, nor reacted as readily with OPA when sulfite was the reductant. Contamination by ammonia from laboratory and shipboard sources complicates application of the method to natural waters, especially measurement of low concentrations (<100 nM) in open-ocean waters. Steps to overcome contamination are described in detail. Some results are presented for ammonium determination in Southern Ocean and Huon Estuary (Tasmania) waters.     

Total petroleum hydrocarbon distribution in soils and groundwater in Songyuan oilfield, Northeast China

In order to investigate the distribution of the total petroleum hydrocarbons (TPH) in groundwater and soil, a total of 71 groundwater samples (26 unconfined groundwater samples, 37 confined groundwater samples, and 8 deeper confined groundwater samples) and 80 soil samples were collected in the Songyuan oilfield, Northeast China, and the vertical variation and spatial variability of TPH in groundwater and soil were assessed. For the groundwater from the unconfined aquifer, petroleum hydrocarbons were not detected in three samples, and for the other 23 samples, concentrations were in the range 0.01–1.74 mg/l. In the groundwater from the confined aquifer, petroleum hydrocarbons were not detected in two samples, and in the other 35 samples, the concentrations were 0.04–0.82 mg/l. The TPH concentration in unconfined aquifer may be influenced by polluted surface water and polluted soil; for confined aquifer, the injection wells leakage and left open hole wells may be mainly responsible for the pollution. For soils, the concentrations of TPH varied with sampling depth and were 0–15 cm (average concentration, 0.63 mg/g), >40–55 cm (average concentration, 0.36 mg/g), >100–115 cm (average concentration, 0.29 mg/g), and >500–515 cm (average concentration, 0.26 mg/g). The results showed that oil spillage and losses were possibly the main sources of TPH in soil. The consequences concluded here suggested that counter measures such as remediation and long-term monitoring should be commenced in the near future, and effective measures should be taken to assure that the oilfields area would not be a threat to human health.     

Offshore drilling effects in Brazilian SE marine sediments: a meta-analytical approach

The exploration and production of oil and gas reserves often result to drill cutting accumulations on the seafloor adjacent to drill locations. In this study, the detection of drilling influence on marine sediments was performed by meta-analytical comparison between data from pre- and post-drilling surveys undertaken in offshore Campos Basin, southeast of Brazil. Besides this overall appraisal on the geochemical variables, a multivariate assessment, considering only the post-drilling data, was performed. Among the variables, fines content, carbonates, total organic carbon, barium, chromium, copper, iron, manganese, nickel, lead, vanadium, zinc, and total petroleum hydrocarbons, only barium, copper, and hydrocarbons were related to drilling impacts. In relation to the point of discharge, relative elevated levels in the post-drilling campaigns were observed preferentially up to 500 m in the northeast and southwest directions, associated to the Brazil Current-predominant direction. Other distributed concentrations in the surroundings seem to indicate the dilution and dispersion of drilling waste promoted by meteoceanographic factors.     

Antimicrobial resistance of heterotrophic marine bacteria isolated from seawater and sands of recreational beaches with different organic pollution levels in southeastern Brazil: evidences of resistance dissemination

Antimicrobial resistance of marine heterotrophic bacteria to different antimicrobials agents were evaluated in seawater, dry and wet sands from three marine recreational beaches with different pollution levels. In all studied beaches, the greatest frequencies of resistance were found in relation to penicillin. On Gonzaguinha, the most polluted beach, 72.3% of all isolated strains showed simple resistance, whilst 8.33% had multiple resistance. The values found on Ilha Porchat beach, were 70.8% and 6.9% for simple and multiple resistances, respectively. On Guaraú, the less polluted beach, only 35.3% of isolated strains had simple resistance. Multiple resistance was not observed. While samples from Gonzaguinha and Ilha Porchat beach showed isolated strains resistant to seven and six different antimicrobial agents, respectively, samples from Guaraú beach were resistant only to penicillin and erytromicin. The positive correlations obtained between the degree of seawater contamination and frequency and variability of bacterial resistance indicate that polluted marine recreational waters and sands are sources of resistant bacteria contributing thus, to the dissemination of bacterial resistance.     

2019年连云港近岸海域水质环境分析与综合评价

于2019年春、夏、秋季对连云港近岸海域海水中营养盐、重金属等共19项指标进行3个航次采样监测。依照海水水质评价标准统计分析站点达标率,采用有机污染物指数法和富营养化指数法,对调查海域海水有机污染、营养水平等进行综合评价。结果表明:2019年连云港市海域站位全年达标率为86.4%,达标面积为6543 km²,占管辖海域面积的98.0%,水质质量较往年有所好转,主要超标物为无机氮、活性磷酸盐。调查海域海水的有机污染和富营养化程度均处于良好状况,近岸海水水质总体上要劣于远岸水质,且随季节的更替呈现波动性变化。     

High-frequency measurements reveal spatial and temporal patterns of dissolved organic matter in an urban water conveyance

Stormwater runoff in urban areas can contribute high concentrations of dissolved organic matter (DOM) to receiving waters, potentially causing impairment to the aquatic ecosystem of urban streams and downstream water bodies. Compositional changes in DOM due to storm events in forested, agricultural, and urban landscapes have been well studied, but in situ sensors have not been widely applied to monitor stormwater contributions in urbanized areas, leaving the spatial and temporal characteristics of DOM within these systems poorly understood. We deployed fluorescent DOM (FDOM) sensors at upstream and downstream locations within a study reach to characterize the spatial and temporal changes in DOM quantity and sources within an urban water conveyance that receives stormwater runoff. Baseflow FDOM decreased over the summer season as seasonal flows upstream transported less DOM. FDOM fluctuated diurnally, the amplitude of which also declined as the summer season progressed. During storms, FDOM concentrations were rapidly elevated to values orders of magnitude greater than baseflow measurements, with greater concentrations at the downstream monitoring site, revealing high contributions from stormwater outfalls between the two locations. Observations from custom, in situ fluorometers resembled results obtained using laboratory methods for identifying DOM source material and indicated that DOM transitioned to a more microbially derived composition as the summer season progressed, while stormwater contributions contributed DOM from terrestrial sources. Deployment of a mobile sensing platform during varying flow conditions captured spatial changes in DOM concentration and composition and revealed contributions of DOM from outfalls during stormflows that would have otherwise been unobserved.     

Survey on fluoride, bromide and chloride contents in public drinking water supplies in Sicily (Italy)

Six hundred and sixty-seven water samples were collected from public drinking water supplies in Sicily and analysed for electric conductivity and for their Cl(-), Br(-) and F(-) contents. The samples were, as far as possible, collected evenly over the entire territory with an average sampling density of about one sample for every 7,600 inhabitants. The contents of Cl(-) and Br(-), ranging between 5.53 and 1,302 mg/l and between <0.025 and 4.76 mg/l respectively, correlated well with the electric conductivity, a parameter used as a proxy for water salinity. The highest values were found both along the NW and SE coasts, which we attributed to seawater contamination, and in the central part of Sicily, which we attributed to evaporitic rock dissolution. The fluoride concentrations ranged from 0.023 to 3.28 mg/l, while the highest values (only three exceeding the maximum admissible concentration of 1.5 mg/l) generally correlated either with the presence in the area of crystalline (volcanic or metamorphic) or evaporitic rocks or with contamination from hydrothermal activity. Apart from these limited cases of exceeding F(-) levels, the waters of public drinking water supplies in Sicily can be considered safe for human consumption for the analysed parameters. Some limited concern could arise from the intake of bromide-rich waters (about 3% exceeding 1 mg/l) because of the potential formation of dangerous disinfection by-products.     

Sources and fate of Salmonella and fecal indicator bacteria in an urban creek

This research aimed to understand the sources and fate of Salmonella and fecal bacteria in urban surface waters. An urban creek (San Pedro Creek, California, USA) that had unusually high levels of Salmonella and fecal bacteria relative to other nearby waterbodies was chosen as a model field site. State of the art microbiological methods were used in concert with modeling to investigate Salmonella and fecal bacteria sources, and determine field-relevant dark inactivation and photoinactivation rates. Three along-creek surveys that spanned reaches adjacent to both urban and forested land covers were conducted to measure Salmonella, enterococci, Escherichia coli, and horse- and human-specific Bacteroidales. Salmonella were detected adjacent to and downstream of urban land cover, but not adjacent to forested land cover. No human or horse-specific Bacteroidales fecal markers were detected implicating other urban animal sources of bacteria. Two locations along the creek where Salmonella was consistently detected were sampled hourly for 25 hours and a mass-balance model was applied to determine field-relevant light and dark inactivation rates for Salmonella, enterococci, and E. coli. Sunlight inactivation did not appear to be important in modulating concentrations of Salmonella, but was important in modulating both enterococci and E. coli concentrations. Dark inactivation was important for all three organisms. This is the first study to quantitatively examine the fate of Salmonella within an urban surface water. Although the work is carried out at a single site, the methodologies are extendable to source tracking in other waterbodies. Additionally, the rate constants determined through the modeling will be useful for modeling these organisms in other surface waters, and represent useful benchmarks for comparison to laboratory-derived inactivation rates.     

Butyltin contamination in sediments and seawater from Kaohsiung Harbor, Taiwan

The distribution of butyltin (BT) compounds in the sediments and seawater, at the river outfalls, fishing ports, shipyards, and industrial zone docks of Kaohsiung Harbor, Taiwan were investigated. Twenty sediment and seawater samples were collected from various locations in the Harbor in 2006 and analyzed for monobutyltin (MBT), dibutyltin (DBT), and tributyltin (TBT). Results showed that the concentration of total BTs varied from 1.5 to 151 ng/g in sediment samples, with TBT being the major component of the sediment samples. This suggests that sediments could be the most possible sink of TBT brought by the sorption mechanism. The concentrations of BTs ranged from 9.7 to 270 ng/L in seawater samples, whereas DBT and MBT, the degradation byproducts of TBT, were mainly the most abundant BT compounds of the seawater samples. This indicates that the abiotic or biotic degradation potential of TBT was significant. Spatially, the highest concentrations of BTs were observed in both water and sediment samples collected from the shipyard and fishing port areas. This indicates that the shipping-related activities (e.g., navigation, ship repair, and ship building) would contribute most of BTs in the environment. Results show that the concentrations of degradation products (DBT and MBT) were related closely to temperature, salinity, dissolved oxygen (DO), and chlorophyll-a of the seawater. This implies that seasonal changes of the water parameters controlled the degradation of TBT in seawater. The observed levels of BT compounds in both seawater and sediments were much higher than those required to induce toxic effects on marine organisms, suggesting that appropriate TBT control strategies should be taken in Kaohsiung Harbor.     

Concentrations of dissolved herbicides and pharmaceuticals in a small river in Luxembourg

Urban and agricultural areas affect the hydraulic patterns as well as the water quality of receiving drainage systems, especially of catchments smaller than 50 km(2). Urban runoff is prone to contamination due to pollutants like pesticides or pharmaceuticals. Agricultural areas are possible sources of nutrient and herbicide contamination for receiving water bodies. The pollution is derived from leaching by subsurface flow, as well as wash-off and erosion caused by surface runoff. In the Luxembourgish Mess River catchment, the pharmaceutical and pesticide concentrations are comparable with those detected by other authors in different river systems worldwide. Some investigated pesticide concentrations infringe current regulations. The maximum allowable concentration for diuron of 1.8 μg l(?-?1) is exceeded fourfold by measured 7.41 μg l(?-?1) in a flood event. The load of dissolved pesticides reaching the stream gauge is primarily determined by the amount applied to the surfaces within the catchment area. Storm water runoff from urban areas causes short-lived but high-pollutant concentrations and moderate loads, whereas moderate concentrations and high loads are representative for agricultural inputs to the drainage system. Dissolved herbicides, sulfonamides, tetracyclines, analgesics and hormones can be used as indicators to investigate runoff generation processes, including inputs from anthropogenic sources. The measurements prove that the influence of kinematic wave effects on the relationship between hydrograph and chemographs should not be neglected in smaller basins. The time lag shows that it is not possible to connect analysed substances of defined samples to the corresponding section of the hydrograph.