Evaluation of the effect of data pre-treatment procedures on classical pattern recognition and principal components analysis: a case study for the geographical classification of tea

A simple transformation that uses the half-range and central value has been used as a data pre-treatment procedure for principal component analysis (PCA) and pattern recognition techniques. The results obtained have been compared with the results from classical normalisation of data (mean normalisation, maximum normalisation and range normalisation), autoscaling and the minimum-maximum transformation. Three data sets were used in the study. The first was formed by determining 17 elements in 53 tea samples (901 pieces of data). The second and third data sets arose from two long-term drift studies performed to examine instrumental stability at standard and robust conditions. The instruments used were an inductively coupled plasma atomic emission spectrometer and an inductively coupled plasma mass spectrometer. Each drift diagnosis experiment consisted of replicate determinations of a test solution containing 15 analytes at 10 mg l-1 over 8 h without recalibration. Twenty-nine emission lines were determined 99 times, thus, each data set was formed by 2881 pieces of data. Data pre-treatment was applied to the three data sets prior to the use of principal component analysis, cluster analysis, linear discrimination analysis and soft independent modelling of class analogy. The study revealed that the half-range and central value transformation resulted in a better classification of the tea samples than that achieved using the classical normalisation. The loadings in the PCA for the long-term stability study, under both standard and robust conditions, were found to be similar to the drift trends only when the minimum-maximum transformation and the mean or maximum normalizations were used as data pre-treatments.     

Sediments as a potential tool for assessment of sewage pollution in Barigüi River, Brazil

Sediments constitute a pollutant trap and have proven to be an efficient tool to identify environmental impacts. Sediments are considered a very important means to assess the level of contamination of water bodies because of their ability to accumulate metals and organic. The anthropogenic inputs of sewage, with or without prior treatment, in aquatic environments, affect the geochemical composition of sediment. In addition, the sediment adsorbs hydrophobic compounds found in feces, such as the fecal sterols. The granulometric and geochemical composition of the sediment of Barigüi River-Brazil was investigated. The results show that silt and clay dominate the granulometric composition of the sediments. The geochemical composition of sediments showed high concentrations of phosphorus and nitrogen. The Redfield ratios confirm the inputs of phosphorus and nitrogen. The TOC/N ratio was used to identify the source of pollution. N/TP ratios were found between 1.0 and 3.5. Clearly, an input of phosphorus, sewage is the most acceptable source, following the historic profile of the Barigüi River. High concentration of nitrogen phosphorus labels the area to be polluted by sewage. To confirm the sewage pollution, adsorbed fecal sterols in sediments were investigated. The concentration of total sterols was found between 0.86 and 304.58 μg g^???1. Two distinguished scenario was found, one severely polluted and another slightly polluted. The highest concentrations of total fecal sterols were associated with sediment whose geochemical composition showed higher levels of TOC, as well as higher proportions of silt and clay. Also, epicoprostanol, a coprostanol isomer, was used as an indicator of the level of treatment or age of the fecal matter because it is formed during the treatment of wastewater and sludge digestion. If the treatment of sludge takes a long time, epicoprostanol can form from cholesterol, and relative proportions of those compounds may be used as an indicator of the presence of untreated sewage in the sediments. The epicoprostanol was found in the range between 0.02 and 9.71 μg g^???1; concentration of up to 0.015 μg g^???1 represents situations where there is strong contamination by sewage. All sites investigated showed a concentration of epicoprostanol higher than the value adopted as threshold. The lower concentration of epicoprostanol found for all sites is consistent with the high concentration found for coprostanol, and this is typical for untreated sewage.     

Mercury in the sediments of Vembanad Lake,western coast of India

Mercury, a global pollutant, is popping up in places where it was never expected before and it burdens in sediments and other non-biological materials. It is estimated to have increased up to five times the pre-human level due to anthropogenic activities. Vembanad backwaters, one of the largest Ramsar site in India, which have extraordinary importance for its hydrological function, are now considered as one of the mercury hot spots in India. In this study, surface sediment samples of Vembanad Lake and nearshore areas have been seasonally analysed for total mercury and methyl mercury concentrations while the core sediment samples were analysed for total mercury. The results showed that the northern part of the lake was more contaminated with mercury than the southern part. The mercury concentration was relatively high in the subsurface sediment samples, indicating the possibility of historic industrial mercury deposition. A decreasing trend in the mercury level towards the surface in the core sediment was also observed. The geochemical parameters were also analysed to understand the sediment mercury chemistry. Anoxic conditions, pH and organic carbon, sulphur and Fe determined the presence of various species of mercury in the sediments of Vembanad Lake. The prevailing physical and geochemical conditions in Vembanad Lake have indicated the chances of chemical transformation of mercury and the potential hazard if the deposited mercury fractions are remobilised.     

Observation of saltwater intrusion and ETM dynamics in a stably stratified estuary: the Yangtze Estuary,China

Spatial and temporal measurement data describing spring–neap variations of velocity, salinity, and suspended sediment concentration (SSC) in the North Passage Deepwater Navigational Channel (DNC) of the Yangtze Estuary, China, were obtained in the wet season of 2012. These data were collected in the middle of the DNC and apparently document the formation of a rather stable density stratification interface and salt wedge, especially during neap tides and slack waters. The convergent zone of residual currents, salinity transport, and sediment transport during neap and spring tides oscillates in the middle and lower reach of the DNC. It encourages the formation of a near-bed high-SSC layer, which favours siltation in the dredged channel. Both the near-bed gradient Richardson number and the bulk/layer Richardson number vary dramatically from around zero to several hundred from spring to neap tides. Stratification and turbulence damping effects near the estuarine turbidity maximum (ETM) area induce the upper half (near water surface) of the water body to be ebb-dominant and the lower part (near-bed) to be flood-dominant, which is a previously undocumented phenomenon in this region. These data reveal that the residual pattern of currents, salt flux and sediment flux are of critical differences in a stratified estuary, and that the salinity-induced baroclinic pressure gradient is a major factor controlling the vertical velocity structure. In addition, field observations indicate that the salinity and sediment transport of residuals generated by internal tidal asymmetry plays a dominant role in maintaining a stable density stratification interface near the estuarine front.     

Normalization procedures for sediment contaminants in spatial and temporal trend monitoring

Rational pollution, or the effectiveness of natural attenuation assessments based upon estimating the degree of contamination, critically depends on the basis of a sound normalization to take into account heterogeneous sedimentary environments. By normalizing the measured contaminant concentration patterns for the sediment characteristics, the inherent variability can be reduced and so allow a more meaningful assessment of both the spatial distributions and the temporal trends. A brief overview and guidance in the methodology available for choosing an appropriate site-specific normalization approach is presented. This is followed by general recommendations with respect to the choice of normalizer and the necessary geochemical and statistical quality assurance methods, with support from the results of recent international intercomparison exercises within the QUASH (Quality Assurance of Sample Handling) programme, as well as discussions within the International Commission on the Exploration of the Sea (ICES) working groups. The most important of these recommendations is the use of a two-tiered normalization approach including wet sieving (<63 microm), followed by an additional geochemical co-factor normalization.     

Polycyclic aromatic hydrocarbons (PAHs) in surface sediments from the Bizerte Lagoon,Tunisia: levels,sources, and toxicological significance

To assess the status of polycyclic aromatic hydrocarbon (PAH) contamination in sediments from the Bizerte Lagoon (northern Tunisia), 18 surface sediment samples were collected in March 2011 and analyzed for 14 US Environmental Protection Agency priority PAHs by high-performance liquid chromatography. The total concentrations of the 14 PAHs (ΣPAHs) ranged from 16.9 to 394.1 ng g^?1 dry weight (dw) with a mean concentration of 85.5 ng g^?1 dw. Compared with other lagoons, coasts, and bays in the world, the concentrations of PAHs in surface sediments of the Bizerte Lagoon are low to moderate. The PAHs’ composition pattern was dominated by the presence of four-ring PAHs (45.8 %) followed by five-ring (26.8 %) and three-ring PAHs (12.7 %). The PAH source analysis suggested that the main origin of PAHs in the sediments of the lagoon was mainly from pyrolytic sources. According to the numerical effect-based sediment quality guidelines of the USA, the levels of PAHs in the Bizerte Lagoon should not exert adverse biological effects. The total benzo[a]pyrene toxicity equivalent values calculated for the samples varied from 3.1 to 53.7 ng g^?1 dw with an average of 10.6 ng g^?1 dw.     

Soils and sediments of the Thua Thien-Hue Province (central Vietnam): recognizing trace element sources and the likely influence of natural events

Trace element concentrations have been measured in soil and sediment samples taken from the Thua Thien Hue (TT-H) Province and the Tam Giang-Cau Hai (TG-CH) Lagoon in 2002 and 2004. Results show that the lagoon is only slightly contaminated by elements such as Ag, Cd, Cr, Cu, Ni, Pb and Zn, whereas As, probably naturally enriched in this Asian region, reaches values above the lowest internationally accepted sediment quality guidelines. Concentrations in soils are ascribable to natural sources and distributions in the TG-CH Lagoon are mainly influenced by river inputs, with Ag and Cd undergoing estuarine desorption processes. However, concentration-depth profiles of most trace elements in sediments show a recent increasing trend that might be linked to the economic development of the area. The comparison of porosity and (210)Pb depth profiles (confirmed also by Cd and As) from repeated samplings of the same core locations in the TG-CH Lagoon seems to account for a loss of 5-10 cm of surficial sediment that took place during the time interval between the two samplings. It is hypothesized that extreme meteorological events (e.g. a major typhoon that hit the area in November 2003) could be responsible for such sediment displacement.     

Ecotoxicological impact assessment of some heavy metals and their distribution in some fractions of mangrove sediments from Red Sea, Egypt

The total and fraction concentrations of heavy metals (Mn, Cu, Ni, Pb, Co, and Cd) were analyzed in some sediment fractions (Φ2, Φ3, Φ4, Φ5) of selected mangrove ecosystems collected from the Egyptian Red Sea shoreline. The results revealed that manganese had the highest mean value (133?±?97 mg/kg) followed by copper (49.9?±?46.0 mg/kg), nickel (28.1?±?11.8 mg/kg), lead (19?±?13 mg/kg), cobalt (6.7?±?4.0 mg/kg), and cadmium (3.327?±?1.280 mg/kg). The concentrations of heavy metals in the different sediment fractions showed that there was a preferential accumulation of Cu, Co, Mn, and to a lesser degree Cd in the silt and clay fractions rather than in the sand-sized. The sediment quality was performed by using some sediment quality guidelines. Additionally, the contamination and the risk assessment of these heavy metals were achieved by different methods including, potential ecological risk index, contamination factor, pollution load index, and geoaccumulation index. According to the Sediment Quality Guidelines comparisons, the concentrations of Mn and Pb were low and showed no possibility of detrimental effects on the local environment. The levels of Cu and Ni were high, however, could not be considered to present serious threat to the mangrove ecosystem. The data showed that the mangrove ecosystems were affected by the Cd risk.     

Abundances, distribution, and sources of trace metals in Nakaumi–Honjo coastal lagoon sediments, Japan

Bottom sediments from Nakaumi Lagoon and the Honjo Area in southwest Japan were analyzed to determine their geochemical compositions and to assess potential impacts by comparison with sediment quality guidelines. Present-day water quality was also assessed. Results showed that the water quality of Nakaumi Lagoon and the Honjo area contrasts between their upper and lower parts. Average abundances of As, Pb, Zn, Cu, Ni, and Cr in the Nakaumi sediments were 12, 25, 135, 32, 21, and 46 ppm, respectively, compared to 10, 24, 110, 26, 20, and 38 ppm in the Honjo area. All averages are greater than those of the upper continental crust. The elevated metal concentrations are probably related to the fine-grained nature of the sediments, reducing bottom conditions produced by abundant organic matter and possibly minor non-point anthropogenic sources. Trace metal contents are strongly correlated with Fe₂O₃, suggesting that Fe oxides play a role in controlling abundances. Metal concentrations exceed the NYSDEC lowest effect level and CCME interim sediment quality guidelines that indicate moderate impact on aquatic organisms. Average abundances of As and Zn are comparable to the Coastal Ocean Sediment Database threshold, whereas maximum concentrations exceed that value, indicating that the concentrations of these metals are potentially toxic. These enrichments suggest that regular monitoring may be desirable even where no point sources of metal pollution exist.     

Identification of dredged sediment-derived soils in the alluvial plains of the Leie and the Upper and Sea Scheldt rivers (Belgium) based on physico-chemical soil properties

An approach was developed to identify surface soils affected by historical dredged sediment disposal in the alluvial plains of the Upper Scheldt, the Sea Scheldt and the Leie river. Dredged sediment-derived soils were identified based on field observations, comparative granulometric analyses and chemical analyses. Criteria developed were based on a comparison between reference data from 102 aerobic soil samples of areas known to be affected by dredged sediment disposal and 104 samples from undisturbed alluvial soils along the studied rivers. A comparative grain size analysis with optical laser diffractometry between the A and C horizon proved useful for the identification of levelled-up sites. The chemical soil characteristics that were most useful in identifying dredged sediment-derived soils were CaCO3, sulfur (S), organic carbon (OC) and phosphorus (P) contents, electrical conductivity (EC), and the C/P and C/S ratios. Criteria for concluding the origin of an investigated soil were specific for the studied area, but the approach presented may provide useful guidelines for developing criteria valid for different regions.     

Sediment composition and normalisation procedures: an example from a QUASH project sediment exercise

The QUASH UE-Project was designed to assess the reliability of normalisation approaches to compensate the influence of natural process affecting the distribution and concentration of contaminants in sediment. The focus of this paper was to test the influence on normalisation procedures of an inorganic matrix using a sample collected in the Venice Lagoon, Italy.     

Relating Benthic Infaunal Community Structure to Environmental Variables in Estuaries using Nonmetric Multidimensional Scaling and Similarity Analysis

In 1994, 19 stations were sampled (2 replicates/station) with Young grabs in association with the EMAP-Estuaries Carolian Province Base Monitoring in Florida. A total of 295 unique benthic infauna taxa and 9647 individuals were identified and enumerated. Environmental data (bottom-water quality, sediment grain size, sediment metals, and organics) and benthic community data were analyzed using hierarchical agglomerative cluster analysis and ordination via nonmetric multidimensional scaling. Bray-Curtis similarities and Euclidean distance were used as the distance measures for biotic and abiotic data, respectively. Multivariate analyses were complemented by examining incremental contributions of benthic taxa to similarity values using a percentage similarity technique. A low-salinity site in a tributary to the St. Johns River had benthic communities uniquely different from those of moderate-to high-salinity sites. A diverse assemblage of polychaetes, gastropods, bivalves, amphipods, sipunculans, and phoronids was consistently associated with relatively unimpacted sites in the Indian River Lagoon. Infaunal community structure in the northern portion of the study area was influenced by the nearby Atlantic Ocean. Community shifts in association with latitudinal gradients and concentrations of sediment metals and organics were apparent. The nonparametric multivariate techniques used in this study were particularly effective at delineating and defining fine-scale community differences.     

Elucidation of the tidal influence on bacterial populations in a monsoon influenced estuary through simultaneous observations

The influence of tides on bacterial populations in a monsoon influenced tropical estuary was assessed through fine resolution sampling (1 to 3 h) during spring and neap tides from mouth to the freshwater end at four stations during pre-monsoon, monsoon and post-monsoon seasons. Higher abundance of total bacterial count (TBC) in surface water near the river mouth, compared to the upstream, during pre-monsoon was followed by an opposite scenario during the monsoon When seasonally compared, it was during the post-monsoon season when TBC in surface water was highest, with simultaneous decrease in their count in the river sediment. The total viable bacterial count (TVC) was influenced by the depth-wise stratification of salinity, which varied with tidal fluctuation, usually high and low during the neap and spring tides respectively. The abundance of both the autochthonous Vibrio spp. and allochthonous coliform bacteria was influenced by the concentrations of dissolved nutrients and suspended particulate matter (SPM). It is concluded that depending on the interplay of riverine discharge and tidal amplitude, sediment re-suspension mediated increase in SPM significantly regulates bacteria populations in the estuarine water, urging the need of systematic regular monitoring for better prediction of related hazards, including those associated with the rise in pathogenic Vibrio spp. in the changing climatic scenarios.     

重金属在贾鲁河表层沉积物中的污染特征及来源分析

采用原子吸收分光光度法、原子荧光法和电感耦合等离子体发射光谱法测定了贾鲁河表层沉积物中6种重金属的含量,用灼烧法测定贾鲁河表层沉积物中有机质含量。运用地累积指数法对贾鲁河流域表层沉积物中重金属污染状况进行评价,并且通过主成分分析法研究贾鲁河重金属污染来源。结果表明：贾鲁河表层沉积物中As、Cu、Ni、Zn的含量比2004年淮河表层沉积物中相应重金属含量明显偏高。重金属污染程度为：As〉Cu〉Zn〉Pb〉Ni〉Cr。通过主成分分析进一步对重金属来源的确定,发现前2个主成分的贡献率分别为58．85％和19．74％,污染来源主要有两类,分别是工农业、生活排污的点源污染,自然变化对沉积物的影响,岩石风化与侵蚀过程和有机质降解矿化的内源污染。     

Characterisation of trace elements and methylmercury in an estuarine sediment reference material, IAEA-405

An estuarine sediment sample, IAEA-405, was recently characterised for trace elements and methylmercury (MeHg) for ultimate use as a marine reference material. The reference values were calculated using data sets from 120 laboratories that participated in a world-wide intercomparison exercise. The data evaluation is highlighted, and includes comparisons of different analytical methods, as well as the distribution of data. Overall laboratory performance for this exercise was encouraging: 86 laboratories (72%) reported data with <25% outliers. There was sufficient acceptable data to establish recommended values for 17 elements and information values for a further 15 elements. In addition, a recommended value was established for methylmercury. The estuarine sediment sample, IAEA-405, can be used as a reference material for quality control in the determination of trace elements and methylmercury in moderately polluted sediments.     

Major ion chemistry and weathering processes in the Midyan Basin, northwestern Saudi Arabia

Chemical characteristics of 72 groundwater samples collected from Midyan Basin have been studied to evaluate major ion chemistry together with the geochemical and weathering processes controlling the water composition. Water chemistry of the study area is mainly dominated by Na, Ca, SO₄, and Cl. The molar ratios of (Ca?+?Mg)/total cations, (Na?+?K)/total cations, (Ca?+?Mg)/(Na?+?K), (Ca?+?Mg)/(HCO₃?+?SO₄), (Ca?+?Mg)/HCO₃, and Na/Cl reveal that water chemistry of the Midyan Basin is controlled by evaporite dissolution (gypsum and/or anhydrite, and halite), silicate weathering, and minor contribution of carbonate weathering. The studied groundwater samples are largely undersaturated with respect to dolomite, gypsum, and anhydrite. These waters are capable of dissolving more of these minerals under suitable physicochemical conditions.     

Assessment of metal enrichments in tsunamigenic sediments of Pichavaram mangroves, southeast coast of India

The 26 December 2004-Tsunami has deposited sediments in the Pichavaram mangrove ecosystem, east coast of India. Ten surface and three core sediment samples were collected within thirty days of the event. High concentrations of Cd, Cu, Cr, Pb, and Ni were observed in the tsunamigenic sediments. With respect to Fe, Zn, and Mn, there was little variation as compared to pre-tsunami values. The geo-accumulation index was calculated in order to assess the contamination of heavy metals in the sediments. The sediments were extremely contaminated with respect to Cd and they showed moderate to strong contamination with respect to Cr, Pb and Ni. The study highlighted the future risk of enhanced metal pollution in near future in this mangrove ecosystem.     

Spatial variation of acid-volatile sulfide and simultaneously extracted metals in Egyptian Mediterranean Sea lagoon sediments

In risk assessment of aquatic sediments, the immobilizing effect of acid-volatile sulfide (AVS) on trace metals is a principal control on availability and associated toxicity of metals to aquatic biota, which reduces metal bioavailability and toxicity by binding and immobilizing metals as insoluble sulfides. Spatial variation pattern of AVS, simultaneously extracted metals (SEM), and sediment characteristics were studied for the first time in surface sediment samples (0–20 cm) from 43 locations in Egyptian northern delta lagoons (Manzalah, Burullus, and Maryut) as predictors of the bioavailability of some divalent metals (Cu, Zn, Cd, Pb, and Ni) in sediments as well as indicators of metal toxicity in anaerobic sediments. The results indicated that the ∑SEM (Cu?+?Zn?+?Cd?+?Pb?+?Ni) values in sediments of lagoon Burullus had higher concentrations than those of Maryut and Manzalah. In contrast, AVS concentrations were considerably higher in lagoons Manzalah and Maryut and seemed to be consistent with the increase in organic matter than lagoon Burullus. Generally, the average concentrations of the SEM in all lagoons were in the order of Zn?>?Cu?>?Ni?>?Pb?>?Cd. The ratios of ∑SEM/AVS were less than 1 at all the sampling stations except at one station in lagoon Maryut as well as four stations located in lagoon Burullus (∑SEM/AVS?>?1), which suggests that the metals have toxicity potential in these sediments. Therefore, SEM concentrations probably are better indicators of the metal bioavailability in sediments than the conventional total metal concentrations.     

Distribution and contamination assessment of heavy metals in sediment of the Second Songhua River, China

The Second Songhua River was subjected to a large amount of raw or primary effluent from chemical industries in Jilin city in 1960s to 1970s, resulting in serious mercury pollution. However, an understanding of other trace metal pollution has remained unclear. The objective of this study was to investigate trace metal contamination in the sediment of the river. Bottom sediment samples were taken in the river between Jilin city and Haerbin city in 2005. An uncontaminated sediment profile was taken in the Nen River at the same time. Total concentrations of Al, Fe, Mg, Ca, K, Na, Ti, Mn, V, Sc, Co, Cu, Cr, Ni, Pb and Zn in the sediment samples were measured by ICP-MS or ICP-OES, following digestion with various acids. Concentrations of Co, Cu, Cr, Ni, Pb and Zn in the surface sediments were 5.1–14.7, 18.5–78.9, 2.4–75.4, 7.2–29.0, 13.5–124.4, and 21.8–403.1 mg/kg, respectively, generally decreasing along the course of the river from Jilin city to Haerbin city. Background concentrations of trace metals were reconstructed by geochemical normalization to a conservative element scandium. Results showed that concentrations of Co, Cr, and Ni in the sediment were generally only slightly higher than or equal to their background values, while concentrations of Cu, Pb, and Zn in the some sediment samples were significantly higher than their background values. In detail, the sediment at Jilin city was moderately contaminated by Cu, and the sediment of the Second Songhua River was moderately contaminated by Pb and Zn. The top layer (0–10 cm depth) and bottom layers (30–46 cm depth) of one sediment profile at Wukeshu town were generally moderately polluted by Pb and Zn. Synthetically, the surface sediment in the studied river section was classified as natural sediment without ecological risk by the sediment pollution index (SPI) of Cu, Cr, Ni, Pb and Zn. Only the 30–45 cm depth of the sediment profile at Wukeshu town was classified as low polluted sediment by the SPI of these metals, recording a historical contamination of the river in the 1960s to 1970s. This buried contamination of trace metals might pose a potential risk to water column under disturbance of sediment. Foundation item: The National Basic Research Priorities Program of China (2004CB418502)     

Observational and modeling study of dry deposition on surrogate surfaces in a South China city: implication of removal of atmospheric crustal particles

Dry deposition samples collected during 1999–2001 at a South China site using surrogate surfaces were analyzed by capillary electrophoresis. Collector surface properties played important roles to the dry deposition. The deposition velocities for various species ranged from 0.02 to 1.69 cm s^???1, in general agreement with literature values. More than 90% of Ca^2?+? was deposited by sedimentation and its comparable values of dry or wet removal residence times imply that dry deposition is an important atmospheric removal process for the ubiquitous crustal species in South China, compared with precipitation scavenging. Relatively good agreement was found when the species deposition velocities were modeled based on up-to-date knowledge of particle dry deposition. The total depositions for anthropogenic and crustal species in northern China are likely to be much higher than those in the south, including our site where the fluxes of the acidic species SO₄ ^2??? and NO₃ ^??? were 4.4 and 2.2 g m^???2 year^???1, respectively. The sum of dry deposition for cations Na^?+?, Ca^2?+?, Mg^2?+?, and K^?+? contributes 44% of the total flux, which is equivalent to the value estimated in Europe.