Estimation of Similarity in the Qualitative Composition of Humic Substance in Marine Sediments By Means of an Uv-Spectroscopic Library

In this paper a method for the study of the qualitative similarity of extractable humic substance (EHS) in marine sediments based on the realisation of UV spectral library of EHS is described. the spectral library was built including the digitised spectra of humic substance extracted from several marine sediments (46 samples) and two samples of standard materials (lignin sulphonate and humic substance) in a Statistica data file. the data matrix was elaborated by means of different multivariate statistic techniques such as Cluster Analysis (CA), Principal Components Analysis (PCA) and the univariate technique Spectral Correlation Analysis (SCA). This approach allows us to show the contribution of different organic compounds (aromatic, lipid and acid) to the composition of EHS and moreover it evidences also the structural characteristics of EHS in terms of similarities in the qualitative composition of samples such as presence of terrestrial and/or vegetal contributions. the UV library is an objective tool to study the qualitative composition of EHS and it represents a complementary approach to the most common methods based on the application of spectroscopic (IR, ¹³CNMR), potentiometric and chromatographic techniques.     

Species of Trace Metals,Organic Residues and Humic Substances in Sediments From the Taiwan Erhjin River and Coastal Areas

Abstract

Total organic carbon, humic substances, and the species of trace metals (including Cu, Zn, Pb, Cd, Cr, Mn and Fe) in six and seven phases, such as bioexchangeable (P1), skeletal (carbonates, P2), easily reducible (Fe and Mn oxides, P3), moderately reducible (crystalline Mn oxides, P4), organic matters with sulphides (P5), and detritus with minerals (P6) as well as organic with humic substances (PB4) and organic residues (PB6), were analyzed in sediments from the Taiwan Erhjin coastal (including river and estuarine) area, where places we found the copper pollution. Results indicate that higher percentages of P1 and P2 for copper, zinc, lead, cadmium and manganese in samples collected in March and September of 1990 were much higher than those in P3-P6. High percentages of chromium and iron in samples respectively collected in March and September of 1990 were found in P6. for the seven phase analysis, higher percentages of copper species in PB4 and PB6 as well as iron species in PB7 were observed. On the other hand, purified humic acid with the high contents of manganese and iron in humic acid as well as purified fulvic acids were generally found at the upstream stations; and low values at coastal stations. However, extremely high copper (as high as 1750μg g^?1, dry weight in fulvic acid and 820μg g^?1 in humic acid) and lead (821μg g^?1 in humic acid) concentrations with relatively high manganese and iron concentrations were observed in humic substances from the station near the copper recycling area. Comparing the results obtained from the Antarctic Ocean sediments with those from the Taiwan Erhjin Chi coastal sediments, the human impacts on the latter are evaluated.     

Influence of the mineralogical composition on microbial activities in marine sediments: an experimental approach

We investigated the influence of the mineralogical composition of marine sediments on bacterial activity in experimental microcosms. Calcite and quartz were added to natural marine sediments and microbial response in terms of total bacterial abundance and biomass, β-D-glucosidase exo-enzymatic activity and bacterial incorporation of a radio-labelled (³H-leucine) substrate were investigated for a period of one month. We report here that after 15 days the mineralogical composition of the sediment (calcite vs. quartz) had an impact on bacterial abundance and activity (reduced for ca 15% and 56%, respectively). However, such impact was mitigated or even disappeared in high organic nutrient conditions.     

Investigations of some trace elements in the Bay of Lim

Sea water was collected at several stations in the Bay of Lim at a depth of one meter below the surface, and before analysis, was filtered with 0.45-μm Millipore filters. Shallow water sediments were collected at the same locations. Humic acids used in this work were separated from near-shore sediments taken from various saline waters of the Bay of Lim. The prepared humic acids were then analysed for their elementary composition and also for positions of their hydrolytic products to obtain more data on how and to which characteristic part, the trace elements were related. The hydrolysis of humic acids was done by chemical methods in order to obtain four main components: amino acids, sugars, phenols and condensed benzene core. Neutron activation analysis was used for trace element analysis in evaporated portions of filtered sea water, sediments, soil, living organisms, humic acids and their hydrolytic products. This work was undertaken to obtain more data on the organic matter present in sediments and in seagrass flats, and also to collect more data on trace elements that are associated with typical and representative samples for the Bay of Lim. Analyses of trace elements associated with either humic acids or their hydrolytic products were performed with the purpose of gaining evidence as to which part of humic acids metals are bound. Humic acids or their decomposition products play an important role in the distribution and availability of a number of essential or nonessential trace elements. Results of this work indicate that humic acids influence the process of redistribution of trace elements in the investigated local coastal area.     

Humic substances as surfactants

Humic substances from soils and sediments can be defined as surface active substances based on the surface tension measurements. Although there are several micellar structural models of humic substances currently available, few studies evaluating humic substances as surfactants have been conducted to date. Therefore, we evaluated the ability of humic substances and their derivatives to influence surface tension. We found that the ability of a humic substance to influence the surface tension of a solution depends on its origin. Many industrially produced humic materials exerted little or no impact on surface tension, whereas humic substances isolated from natural environments (water, soil, peat, sediments, sludge from wastewater treatment facilities) exerted a large impact on surface tension. These findings indicate that the modification of humic substances can enable their use as surfactants. In addition, these findings indicate that solutions of humic substances and their derivatives can be used to increase the solubility of organic compounds.     

西湖沉积物有机质特征

分析了西湖沉积物腐殖质的组成及腐殖酸的红光谱特性,结果显示西湖沉积物腐殖质具有典型的湖泊沉积物腐质特征,腐殖化程度较高;结合形分析表明,腐殖质中：胡敏素〉胡敏酸〉富里酸〉脂类,钱塘江引水工程、水面种植荷花明显改变了沉积物有机质的构成,对西湖的碳和富营养化状况有显著影响。     

Factors influencing the photodegradation of N-nitrosodimethylamine in drinking water

In order to provide basic data for practical application, photodegradation experiment of N-nitrosodimethylamine (NDMA) in aqueous solution was carried out with a low-pressure Hg lamp. Effects of the initial concentration of NDMA, solution pH, dissolved oxygen, and the presence of humic acid on NDMA photodegradation were investigated. NDMA at various initial concentrations selected in this study was almost completely photodegraded by UV irradiation within 20 min, except that at 1.07 mmol/L, NDMA could be photodegraded almost completely in the acidic and neutral solutions, while the removal efficiency decreased remarkably in the alkaline solution. Dissolved oxygen enhanced the NDMA photodegradation, and the presence of humic acid inhibited the degradation of NDMA. Depending on the initial concentration of NDMA, NDMA photodegradation by UV obeyed the pseudo-first-order kinetics. Dimethylamine, nitrite, and nitrate were detected as the photodegradation products of NDMA. ¹O₂ was found to be the reactive oxygen species present in the NDMA photodegradation process by UV, based on the inhibiting experiments using tert-butanol and sodium azide.     

Species of Trace Metals, Organic Residues and Humic Substances in Sediments From the Taiwan Erhjin River and Coastal Areas

Total organic carbon, humic substances, and the species of trace metals (including Cu, Zn, Pb, Cd, Cr, Mn and Fe) in six and seven phases, such as bioexchangeable (P1), skeletal (carbonates, P2), easily reducible (Fe and Mn oxides, P3), moderately reducible (crystalline Mn oxides, P4), organic matters with sulphides (P5), and detritus with minerals (P6) as well as organic with humic substances (PB4) and organic residues (PB6), were analyzed in sediments from the Taiwan Erhjin coastal (including river and estuarine) area, where places we found the copper pollution. Results indicate that higher percentages of P1 and P2 for copper, zinc, lead, cadmium and manganese in samples collected in March and September of 1990 were much higher than those in P3-P6. High percentages of chromium and iron in samples respectively collected in March and September of 1990 were found in P6. for the seven phase analysis, higher percentages of copper species in PB4 and PB6 as well as iron species in PB7 were observed. On the other hand, purified humic acid with the high contents of manganese and iron in humic acid as well as purified fulvic acids were generally found at the upstream stations; and low values at coastal stations. However, extremely high copper (as high as 1750μg g^-1, dry weight in fulvic acid and 820μg g^-1 in humic acid) and lead (821μg g^-1 in humic acid) concentrations with relatively high manganese and iron concentrations were observed in humic substances from the station near the copper recycling area. Comparing the results obtained from the Antarctic Ocean sediments with those from the Taiwan Erhjin Chi coastal sediments, the human impacts on the latter are evaluated.     

Influence of the mineralogical composition on microbial activities in marine sediments: an experimental approach

We investigated the influence of the mineralogical composition of marine sediments on bacterial activity in experimental microcosms. Calcite and quartz were added to natural marine sediments and microbial response in terms of total bacterial abundance and biomass, β-D-glucosidase exo-enzymatic activity and bacterial incorporation of a radio-labelled (³H-leucine) substrate were investigated for a period of one month. We report here that after 15 days the mineralogical composition of the sediment (calcite vs. quartz) had an impact on bacterial abundance and activity (reduced for ca 15% and 56%, respectively). However, such impact was mitigated or even disappeared in high organic nutrient conditions.     

Chemical Approach to Study the Environmental Implications of Humic Acid and Gamma-Hch Interaction

Pesticide-humic interactions are known to have environmental significance in modifying the toxicity and mobility of agricultural chemicals. to test this, interaction between gamma-hexachlorocyclohexane (gamma-HCH) released from the sand coated with gamma-HCH and humic acid was investigated using thin layer chromatography and spectral studies such as UV (ultraviolet), IR (infrared), mass and FAB (fast atom bombardment) mass spectrometry. These studies revealed the evidence of loose interchelation between gamma-HCH and humic acid. the significance of the results in relation to detoxification of gamma-HCH in aquatic ecosystems are discussed.     

A unified approach for including non-extractable residues (NER) of chemicals and pesticides in the assessment of persistence

All chemicals form non-extractable residues (NER) to various extents in environmental media like soil, sediment, plants and animals. NER can be quantified in environmental fate studies using isotope-labeled (such as ¹⁴C or ¹³C) tracer compounds. Previous NER definitions have led to a mismatch of legislation and state of knowledge in research: the residues are assumed to be either irreversibly bound degradation products or at least parts of these residues can be released. In the latter assumption, soils and sediments are a long-term source of slowly released residues. We here present a conceptual experimental and modeling approach to characterize non-extractable residues and provide guidance how they should be considered in the persistence assessment of chemicals and pesticides. Three types of NER can be experimentally discriminated: sequestered and entrapped residues (type I), containing either the parent substance or xenobiotic transformation products or both and having the potential to be released, which has indeed been observed. Type II NER are residues that are covalently bound to organic matter in soils or sediments or to biological tissue in organisms and that are considered being strongly bound with very low remobilization rates like that of humic matter degradation rates. Type III NER comprises biogenic NER (bioNER) after degradation of the xenobiotic chemical and anabolic formation of natural biomolecules like amino acids and phospholipids, and other biomass compounds. We developed the microbial turnover to biomass (MTB) model to predict the formation of bioNER based on the structural properties of chemicals. Further, we proposed an extraction sequence to obtain a matrix containing only NER. Finally, we summarized experimental methods to distinguish the three NER types. Type I NER and type II NER should be considered as potentially remobilizable residues in persistence assessment but the probability of type II release is much lower than that of type I NER, i.e., type II NER in soil are “operationally spoken” irreversibly bound and can be released only in minute amounts and at very slow rates, if at all. The potential of remobilization can be evaluated by chemical, physical and biological methods. BioNER are of no environmental concern and, therefore, can be assessed as such in persistence assessment. The general concept presented is to consider the total amount of NER minus potential bioNER as the amount of xenoNER, type I?+?II. If a clear differentiation of type I and type II is possible, for the calculation of half-life type I NER are considered as not degraded parent substance or transformation product(s). On the contrary, type II NER may generally be considered as (at least temporarily) removed. Providing proof for type II NER is the most critical issue in NER assessment and requires additional research. If no characterization and additional information on NER are available, it is recommended to assess the total amount as potentially remobilizable. We propose our unified approach of NER characterization and evaluation to be implemented into the persistence and environmental hazard assessment strategies for REACH chemicals and biocides, human and veterinary pharmaceuticals, and pesticides, irrespective of the different regulatory frameworks.     

Effect of natural aquatic humic substances on the photodegradation of bisphenol A

The photochemical degradation of bisphenol A (BPA) was studied in the presence of natural humic substances from different origins under simulated solar irradiation. BPA underwent insignificant direct photolysis in neutral water, but rapid photosensitized degradation in four humic substances solutions via pseudo-first-order reaction occurred. The photo-degradation rate of BPA was insensitive to the different initial BPA concentrations and was inhibited in aerated solution compared with the deoxygenated medium. The reactive oxygen species (ROS) such as ·OH and ¹O₂ produced from excitation of humic substances under irradiation was determined from the quenching kinetic experiment using molecular probe. The five main intermediate photoproducts of BPA in Nordic lake fulvic acid (NOFA) were tentatively identified using gas chromatography/mass spectrometer (GC/MS). Based on the identification of ROS and the analysis of photoproduct formation, the possible phototransformation pathways of BPA were proposed, involving the direct photolysis due to the energy transfer from the triplet state humic substance (³HS*) to BPA molecules and hydroxyl radical addition and oxidation as well.     

Sediment organic matter and meiofauna community response to long-term fish-farm impact in the Ligurian Sea (Western Mediterranean)

Quantitative and qualitative changes in meiofauna community structure were investigated to assess the impact of a fish farm, which was operating continuously for 15 years (La Spezia Gulf, W Mediterranean). Sediment samples were collected in June, July, September, October 2000 and February 2001 for the analysis of phytopigments (chlorophyll-a and phaeopigments), the biochemical composition of organic matter (proteins, carbohydrates and lipids) and related to meiofaunal parameters.

Sediment organic matter reached extremely high concentrations beneath the fish cages when compared to the control. Particularly lipids, carbohydrates and chlorophyll-a were significantly higher in fish-farm sediments. On a long-term basis meiofauna displayed adaptations in sediments beneath the cages resulting in an increase of density. Organic impact on meiofaunal community structure was evident in terms of an increase of the nematodes to copepods (Ne/Co) and nauplius to copepods (Na/Co) ratios in fish farm sediments. Cumaceans and kinorhynchs were encountered in control sediments, but disappeared in fish-farm samples. These data suggest that meiofauna is a sensitive tool for evaluating the effects of organic enrichment in fish farm impacted areas.     

Soil organic matter chemistry. Part 1. Characterization of several humic preparations by proton and carbon‐13 nuclear magnetic resonance spectroscopy

Both laboratory and commercial preparations of humic substances (HSs) such as fulvic acids and humic acids along with HC1‐HF preparation of Manitoba peat soil organic matter were characterized using Fourier Transformation (FT) proton (¹H) and carbon‐13 (¹³C) nuclear magnetic resonance (NMR) spectroscopy. All the samples were dissolved in a solution of 0.4 N NaOD in D₂O. In the case of ‘H‐NMR spectroscopy, all the investigated humic samples displayed resonance absorption peaks in the region of 1–4 ppm indicating the likely presence of aliphatic protons in the preparations. However, with the exception of one fulvic acid preparation (extracted from Manitoba Carrol clay‐loam soil with 0.5 N NaOH), ¹H‐NMR spectra of all other samples provided evidence for strong aromatic character. The aliphatic and aromatic characteristics of such samples of HSs were further confirmed with the aid of ¹³C‐NMR spectra.     

Using vertebrate environmental DNA from seawater in biomonitoring of marine habitats

Conservation and management of marine biodiversity depends on biomonitoring of marine habitats, but current approaches are resource-intensive and require different approaches for different organisms. Environmental DNA (eDNA) extracted from water samples is an efficient and versatile approach to detecting aquatic animals. In the ocean, eDNA composition reflects local fauna at fine spatial scales, but little is known about the effectiveness of eDNA-based monitoring of marine communities at larger scales. We investigated the potential of eDNA to characterize and distinguish marine communities at large spatial scales by comparing vertebrate species composition among marine habitats in Qatar, the Arabian Gulf (also known as the Persian Gulf), based on eDNA metabarcoding of seawater samples. We conducted species accumulation analyses to estimate how much of the vertebrate diversity we detected. We obtained eDNA sequences from a diverse assemblage of marine vertebrates, spanning 191 taxa in 73 families. These included rare and endangered species and covered 36% of the bony fish genera previously recorded in the Gulf. Sites of similar habitat type were also similar in eDNA composition. The species accumulation analyses showed that the number of sample replicates was insufficient for some sampling sites but suggested that a few hundred eDNA samples could potentially capture >90% of the marine vertebrate diversity in the study area. Our results confirm that seawater samples contain habitat-characteristic molecular signatures and that eDNA monitoring can efficiently cover vertebrate diversity at scales relevant to national and regional conservation and management.     

Colonization of meiobenthos in oil-contaminated subtidal sands in the lower Chesapeake Bay

In-situ manipulative experiments were conducted over a 3-month period (May–August 1980) to examine the rate at which meiobenthos colonizes oiled and untreated azoic fine sands at a shallow subtidal site in the lower York River, Virginia. Three concentrations of fresh Prudhoe Bay crude oil were added to sediments: 100, 2 500 and 10000 mg oil kg^-1 dry wt sediment. Untreated azoic and natural sediments served as controls. Within 16 d, meiofauna densities in all treatments were comparable to natural populations in surface oxidized sediments, but densities fluctuated greatly during the remainder of the sampling period. Nematodes slowly colonized the subsurface anoxic sediments below the redox potential discontinuity (RPD); some less common species did not significantly recover below the RPD in the two more heavily oiled treatments. Analysis of nematode community composition by reciprocal averaging ordination and numerical classification revealed generally lower abundances, but no distinct differences, in species composition in the oiled substrates as compared to untreated and natural community controls. Ordination of sequential samples suggested that the nematode species assemblages in the untreated controls fully recovered from these small-scale disturbances by 90 d. Life history characteritics and frequent tidal transport combine to make estuarine meiobenthos highly resilient following disturbance. Contrary to prior recolonization studies, a successional sequence was found for the colonizing nematodes which may be analogous to models of macrobenthic colonization (e.g. McCall, 1975). The comesomatid nematode Sabatieria pulchra, which is frequently dominant in polluted sediments, colonized relatively late in the experiment. Consequently, stress resistance and resilience may not be as coincident in meiofauna as in macrofauna because of differences in factors affecting their dispersal.     

Residues of fluoroquinolones in marine aquaculture environment of the Pearl River Delta, South China

Concentrations and distributions of selected fluoroquinolones (norfloxacin, ciprofloxacin and enrofloxacin) in water, sediments and nine kinds of fish species collected from 6 sites in two marine aquaculture regions of the Pearl River Delta, China, were analyzed by using high-performance liquid chromatography with fluorescence detector (HPLC). The results showed that the concentrations of ciprofloxacin and enrofloxacin were below the limits of quantification (LOQ) in all water samples except for norfloxacin. Norfloxacin and ciprofloxacin concentrations ranged from 1.88 to 11.20 ng g⁻¹ dry wt, 0.76–2.42 ng g⁻¹ dry wt in sediments collected from the Dapeng’ao region (sites 1–3) and ranged from 2.31 to 4.75 ng g⁻¹ dry wt, 1.26–1.76 ng g⁻¹ dry wt in sediments collected from the Hailing Island region (sites 4–6), respectively. However, no enrofloxacin was found in all sediment samples. The three fluoroquinolones (FQs) were detected in all fish samples, and the concentrations were higher in liver tissues than those in muscle tissues. The levels of norfloxacin were higher than ciprofloxacin and enrofloxacin in both liver and muscle tissues. Among the nine marine fish species, Siganus fuscescens from Hailing Island had a significantly high level of norfloxacin in liver tissue (254.58 ng g⁻¹ wet wt), followed by Sparus macrocephalus (133.15 ng g⁻¹ wet wt) from Dapeng’ao, and the lowest value was Lutianus argentimaculatus (5.18 ng g⁻¹ wet wt) from Hailing Island. The obtained results of FQs in present study do not represent a risk to the human health in Guangdong coastal area, based on the maximum residue limits (MRLs) established by Chinese Government and the acceptable daily intake (ADI) recommended by the Food and Agriculture Organization and World Health Organization (FAO/WHO).     

Sources and concentrations of vascular plant material in sediments of Buzzards Bay,Massachusetts, USA

Samples of surface sediment from Buzzards Bay and creek sediment from Great Sippewissett Marsh were analyzed for lignin and stable carbon isotope composition in 1984. The lack of change in composition of lignins in detritus of Spartina alterniflora over two years of decomposition and similar aldehyde/acid ratios of lignin oxidation products of plant and sediment samples indicated minimal diagenesis of lignins in sediments. Remains of non-woody angiosperm tissues made up the bulk of the vascular plant debris in Great Sippewissett Marsh and Buzzards Bay sediments. These plant remains were evenly distributed over the sampling area in Buzzards Bay. Based on model calculations, salt marshes potentially contributed a significant fraction of the total amount of vascular plant debris in coastal marine sediments. The bulk of the organic matter in Buzzards Bay sediments, however, was derived from phytoplankton; vascular plant remains made up only 5 to 7% of the total amount of organic carbon in these sediments.     

Sediment organic matter and meiofauna community response to long-term fish-farm impact in the Ligurian Sea (Western Mediterranean)

Quantitative and qualitative changes in meiofauna community structure were investigated to assess the impact of a fish farm, which was operating continuously for 15 years (La Spezia Gulf, W Mediterranean). Sediment samples were collected in June, July, September, October 2000 and February 2001 for the analysis of phytopigments (chlorophyll-a and phaeopigments), the biochemical composition of organic matter (proteins, carbohydrates and lipids) and related to meiofaunal parameters.

Sediment organic matter reached extremely high concentrations beneath the fish cages when compared to the control. Particularly lipids, carbohydrates and chlorophyll-a were significantly higher in fish-farm sediments. On a long-term basis meiofauna displayed adaptations in sediments beneath the cages resulting in an increase of density. Organic impact on meiofaunal community structure was evident in terms of an increase of the nematodes to copepods (Ne/Co) and nauplius to copepods (Na/Co) ratios in fish farm sediments. Cumaceans and kinorhynchs were encountered in control sediments, but disappeared in fish-farm samples. These data suggest that meiofauna is a sensitive tool for evaluating the effects of organic enrichment in fish farm impacted areas.     

Sources of polycyclic aromatic hydrocarbons (PAHs) in sediments of the Biobio River in south central Chile

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the environment; there are concerns about them due to their toxic properties. Human activities could significantly contribute to the total PAH burden in river sediments. In this work, we document the analysis of PAHs in sediments taken in the middle stretch of the Biobio River in south central Chile. This river is a principal system, draining more than 24,000 km² and subjected to a diverse variety of human-made stressors (pulp mill and urban effluents, agricultural drainage systems, etc). During 2003, several sediment samples were taken in more than 45 sampling sites located in the river’s middle stretch. Due to the granulometric characteristics (mainly sandy sediments), only 17 samples were analyzed, taking into consideration the presence of a fine section within the sediment sample. Using HPLC with fluorescence detection, 15 EPA priority PAHs and perylene were analyzed. The composition of PAHs in the sediment samples is rather similar between sites and levels averaged 104 ± 78 ng g⁻¹ d.w. The highest levels were detected downstream from an industrial discharge. A good correlation was observed between PAH levels and organic carbon content in the tested sediments; however, concentrations above 134 ng g⁻¹ d.w. did not indicate correlation. The samples PAH ratios (Flu/Pyr and Chr/B(a)A) reveal a strong pyrolytic PAH pattern in the sediments tested, supporting evidence indicating that PAHs come mainly from pyrolytic sources. This result contrasts with previous records that have shown a natural influence in the upper basin and a petrogenic pattern near the mouth.