A study of methods used to analyze total oil and polycyclic aromatic hydrocarbons in produced water: steps towards the validation of molecularly imprinted polymers for use in marine environmetns

Produced water is a by-product of offshore oil and gas production, and is released in large volumes when platforms are actively processing crude oil. Some pollutants are not typically removed by conventional oil/water separation methods and are discharged with produced water. Oil and grease can be found dispersed in produced water in the form of tiny droplets, and polycyclic aromatic hydrocarbons (PAHs) are commonly found dissolved in produced water. Both can have acute and chronic toxic effects in marine environments even at low exposure levels. The analysis of the dissolved and dispersed phases are a priority, but effort is required to meet the necessary detection limits. There are several methods for the analysis of produced water for dispersed oil and dissolved PAHs, all of which have advantages and disadvantages. In this work, EPA Method 1664 and APHA Method 5520 C for the determination of oil and grease will be examined and compared. For the detection of PAHs, EPA Method 525 and PAH MIPs will be compared, and results evaluated. APHA Method 5520 C Partition-Infrared Method is a liquid-liquid extraction procedure with IR determination of oil and grease. For analysis on spiked samples of artificial seawater, extraction efficiency ranged from 85 – 97%. Linearity was achieved in the range of 5 – 500 mg/L. This is a single-wavelength method and is unsuitable for quantification of aromatics and other compounds that lack sp³-hybridized carbon atoms. EPA Method 1664 is the liquid-liquid extraction of oil and grease from water samples followed by gravimetric determination. When distilled water spiked with reference oil was extracted by this procedure, extraction efficiency ranged from 28.4 – 86.2%, and %RSD ranged from 7.68 – 38.0%. EPA Method 525 uses solid phase extraction with analysis by GC-MS, and was performed on distilled water and water from St. John’s Harbour, all spiked with naphthalene, fluorene, phenanthrene, and pyrene. The limits of detection in harbour water were 0.144, 3.82, 0.119, and 0.153 g/L respectively. Linearity was obtained in the range of 0.5-10 g/L, and %RSD ranged from 0.36% (fluorene) to 46% (pyrene). Molecularly imprinted polymers (MIPs) are sorbent materials made selective by polymerizing functional monomers and crosslinkers in the presence of a template molecule, usually the analytes of interest or related compounds. They can adsorb and concentrate PAHs from aqueous environments and are combined with methods of analysis including GC-MS, LC-UV-Vis, and desorption electrospray ionization (DESI)- MS. This work examines MIP-based methods as well as those methods previously mentioned which are currently used by the oil and gas industry and government environmental agencies. MIPs are shown to give results consistent with other methods, and are a low-cost alternative improving ease, throughput, and sensitivity. PAH MIPs were used to determine naphthalene spiked into ASTM artificial seawater, as well as produced water from an offshore oil and gas operation. Linearity was achieved in the range studied (0.5 – 5 mg/L) for both matrices, with R² = 0.936 for seawater and R² = 0.819 for produced water. The %RSD for seawater ranged from 6.58 – 50.5% and for produced water, from 8.19 – 79.6%.

(Table 1) Salinity and dissolved organic carbon concentration of marine water (ANT-XIX/2) and mangrove porewater (Brazil)

The chemical structure of refractory marine dissolved organic matter (DOM) is still largely unknown. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS) was used to resolve the complex mixtures of DOM and provide valuable information on elemental compositions on a molecular scale. We characterized and compared DOM from two sharply contrasting aquatic environments, algal-derived DOM from the Weddell Sea (Antarctica) and terrigenous DOM from pore water of a tropical mangrove area in northern Brazil. Several thousand molecular formulas in the mass range of 300-600 Da were identified and reproduced in element ratio plots. On the basis of molecular elemental composition and double-bond equivalents (DBE) we calculated an average composition for marine DOM. O/C ratios in the marine samples were lower (0.36 ± 0.01) than in the mangrove pore-water sample (0.42). A small proportion of chemical formulas with higher molecular mass in the marine samples were characterized by very low O/C and H/C ratios probably reflecting amphiphilic properties. The average number of unsaturations in the marine samples was surprisingly high (DBE = 9.9; mangrove pore water: DBE = 9.4) most likely due to a significant contribution of carbonyl carbon. There was no significant difference in elemental composition between surface and deep-water DOM in the Weddell Sea. Although there were some molecules with unique marine elemental composition, there was a conspicuous degree of similarity between the terrigenous and algal-derived end members. Approximately one third of the molecular formulas were present in all marine as well as in the mangrove samples. We infer that different forms of microbial degradation ultimately lead to similar structural features that are intrinsically refractory, independent of the source of the organic matter and the environmental conditions where degradation took place.

Short-term metabolic and growth responses of the cold-water coral lophelia pertusa to ocean acidification

Cold-water corals are amongst the most three-dimensionally complex deep-sea habitats known and are associated with high local biodiversity. Despite their importance as ecosystem engineers, little is known about how these organisms will respond to projected ocean acidification. Since preindustrial times, average ocean pH has already decreased from 8.2 to ~ 8.1. Predicted CO2 emissions will decrease this by up to another 0.3 pH units by the end of the century. This decrease in pH may have a wide range of impacts upon marine life, and in particular upon calcifiers such as cold-water corals. Lophelia pertusa is the most widespread cold-water coral (CWC) species, frequently found in the North Atlantic. Data here relate to a short term data set (21 days) on metabolism and net calcification rates of freshly collected L. pertusa from Mingulay Reef Complex, Scotland. These data from freshly collected L. pertusa from the Mingulay Reef Complex will help define the impact of ocean acidification upon the growth, physiology and structural integrity of this key reef framework forming species.

Under-ice fauna, sea-ice concentration, sea-ice thickness and under-ice water parameters from the Eurasian central Arctic Ocean during POLARSTERN cruise ARK-XXVII/3 (PS80) in August-September 2012

Arctic sea-ice decline is expected to have a significant impact on Arctic marine ecosystems. Ice-associated fauna play a key role in this context because they constitute a unique part of Arctic biodiversity and transmit carbon from sea-ice algae into pelagic and benthic food webs. Our study presents the first regional-scale record of under-ice faunal distribution and the environmental characteristics of under-ice habitats throughout the Eurasian Basin. Sampling was conducted with a Surface and Under-Ice Trawl, equipped with a sensor array recording ice thickness and other physical parameters during trawling. We identified 2 environmental regimes, broadly coherent with the Nansen and Amundsen Basins. The Nansen Basin regime was distinguished from the Amundsen Basin regime by heavier sea-ice conditions, higher surface salinities and higher nitrate + nitrite concentrations. We found a diverse (28 species) under-ice community throughout the Eurasian Basin. Change in community structure reflected differences in the relative contribution of abundant species. Copepods (Calanus hyperboreus and C. glacialis) dominated in the Nansen Basin regime. In the Amundsen Basin regime, amphipods (Apherusa glacialis, Themisto libellula) dominated. Polar cod Boreogadus saida was present throughout the sampling area. Abrupt changes from a dominance of ice-associated amphipods at ice-covered stations to a dominance of pelagic amphipods (T. libellula) at nearby ice-free stations emphasised the decisive influence of sea ice on small-scale patterns in the surface-layer community. The observed response in community composition to different environmental regimes indicates potential long-term alterations in Arctic marine ecosystems as the Arctic Ocean continues to change.

Climate-Driven Range Shifts Within Benthic Habitats Across a Marine Biogeographic Transition Zone.

Anthropogenic climate change is causing unprecedented rapid responses in marine communities, with species across many different taxonomic groups showing faster shifts in biogeographic ranges than in any other ecosystem. Spatial and temporal trends for many marine species are difficult to quantify, however, due to the lack of long-term datasets across complete geographical distributions and the occurrence of small-scale variability from both natural and anthropogenic drivers. Understanding these changes requires a multidisciplinary approach to bring together patterns identified within long-term datasets and the processes driving those patterns using biologically relevant mechanistic information to accurately attribute cause and effect. This must include likely future biological responses, and detection of the underlying mechanisms in order to scale up from the organismal level to determine how communities and ecosystems are likely to respond across a range of future climate change scenarios. Using this multidisciplinary approach will improve the use of robust science to inform the development of fit-for-purpose policy to effectively manage marine environments in this rapidly changing world.

Climate-Driven Range Shifts Within Benthic Habitats Across a Marine Biogeographic Transition Zone.

Anthropogenic climate change is causing unprecedented rapid responses in marine communities, with species across many different taxonomic groups showing faster shifts in biogeographic ranges than in any other ecosystem. Spatial and temporal trends for many marine species are difficult to quantify, however, due to the lack of long-term datasets across complete geographical distributions and the occurrence of small-scale variability from both natural and anthropogenic drivers. Understanding these changes requires a multidisciplinary approach to bring together patterns identified within long-term datasets and the processes driving those patterns using biologically relevant mechanistic information to accurately attribute cause and effect. This must include likely future biological responses, and detection of the underlying mechanisms in order to scale up from the organismal level to determine how communities and ecosystems are likely to respond across a range of future climate change scenarios. Using this multidisciplinary approach will improve the use of robust science to inform the development of fit-for-purpose policy to effectively manage marine environments in this rapidly changing world.

Studying and measuring the amount of detergents in sea-water samples in order to eliminate with adsorbents and inorganic nano-adsorbents for the sake of securing the water for marine nourishment pools

Increasing the amount of detergent industries in world in spite of having abundant benefits; entering a new kind of contamination into environment and attract the attention of environment liable of different countries to itself. Entering detergents into an aqueous solution cause pollution of water sources and environment in respect of appearing e problem and charges like: nutritive phenomenon, decomposition of hard group of detergent and producing foam. After using Detergents, they were poured into rivers, seas and lakes and have destructive effect on environment. A lot of hygiene problems were attributed to the water having detergents more than allowed value. So, it is specified the importance of eliminating detergents from contaminated water and it is application for secondary use. In order to attain to this aim, we can use inorganic nano and micro-caolin. In this study the adsorptive properties of detergent on the micro and nano caolin adsorbents were studied and the effect of various parameters like the amount of adsorptive materials, initial concentration of detergent, speed of stirring, electrolyte, temperature, time and pH were determined. The surface area of micro- and nano-caoline was reported 11.867 and 49.1438 m2 g-1, respectively. That increasing in nano-caoline surface area confirms increasing in capacity and more rate of adsorption. The results gained by this research recommend using micro- and nano-caolin as a plentiful, available and effective adsorbents. Also in comparison, using nano-caoline was recommended in order to have more effectiveness.

Investigate the effect of antibacterial ingredients used in marine paints in sea water

In this study, consider to the mechanism of controlled depletion paint, has been made the Antifouling (A/F) paints that use these in a paint system which applied on the steel. As a first step, it is necessary to prove that the system subject to investigation does fit into the mechanisms proposed for the CDPs system. According to this, the machine was designed and built as for ASTM D5108-90, D4939-89. Specimens immersed in natural sea water and were rotating by 60 r/min rotor. Painted specimens were tested for 59 days. The main objective of this study was to investigate if new antifouling paint are less toxic than traditional paint and more efficient. For this reason, Zineb and Ziram which is an ingredient in antifouling paints, was also studied. Zineb and Ziram are known as booster biocides in A/P composition. We used the Zineb and Ziram and synthesis of these in a A/F paints. The concentration of booster biocides are 3% and 6% in paints. We use scanning electron microscopy (SEM) for evaluation of paint film. The settlement and the growth of living organism on immersed surfaces was observed during 59 days. According to reports, the growth of organism was observed for A/F paint contains, 3% Zineb after 20days,3%Ziram after 24days and 3% Zineb +Ziram after 30days. By measuring leached rate of the Zn in A/F paints, we figured out the effectiveness of booster biocides on the growth of organism, for example in the absence of booster biocides, the critical released rate for preventing biofilm for A/F paint with ZnO is 15 μg/cm2day. This despite the fact that this figure for A/F paint contain Zineb is 4 μg/cm2, Ziram is 3 μg/cm2 and Zineb +Ziram is 2 μg/cm2.

Determination of thresholds in marine molluscs as an alternative to the Environmental Quality Standards in marine water defined in the Water Framework Directive

The Water Framework Directive (WFD) establishes Environmental Quality Standards (EQS) in marine water for 34 priority substances. Among these substances, 25 are hydrophobic and bioaccumulable (2 metals and 23 organic compounds). For these 25 substances, monitoring in water matrix is not appropriate and an alternative matrix should be developed. Bivalve mollusks, particularly mussels (Mytilus edulis, Mytilus galloprovincialis), are used by Ifremer as a quantitative biological indicator since 1979 in France, to assess the marine water quality. This study has been carried out in order to determine thresholds in mussels at least as protective as EQS in marine water laid down by the WFD. Three steps are defined: - Provide an overview of knowledges about the relations between the concentrations of contaminants in the marine water and mussels through bioaccumulation factor (BAF) and bioconcentration factor (BCF). This allows to examine how a BCF or a BAF can be determined: BCF can be determined experimentally (according to US EPA or ASTM standards), or by Quantitative Activity-Structure Relationship models (QSAR): four equations can be used for mussels. BAF can be determined by field experiment; but none standards exists. It could be determined by using QSAR but this method is considered as invalid for mussels, or by using existing model: Dynamic Budget Model, but this is complex to use. - Collect concentrations data in marine water (Cwater) in bibliography for those 25 substances; and compare them with concentration in mussels (Cmussels) obtained through French monitoring network of chemicals contaminants (ROCCH) and biological integrator network RINBIO. According to available data, this leads to determine the BAF or the BCF (Cmussels /Cwater) with field data. - Compare BAF and BCF values (when available) obtained with various methods for these substances: BCF (stemming from the bibliography, using experimental process), BCF calculated by QSAR and BAF determined using field data. This study points out that experimental BCF data are available for 3 substances (Chlorpyrifos, HCH, Pentachlorobenzene). BCF by QSAR can be calculated for 20 substances. The use of field data allows to evaluate 4 BAF for organic compounds and 2 BAF for metals. Using these BAF or BCF value, thresholds in shellfish can be determined as an alternative to EQS in marine water.

Marine litter in the upper São Vicente submarine canyon (SW Portugal): abundance, distribution, composition and fauna interactions

Marine litter has become a worldwide environmental problem, tainting all ocean habitats. The abundance, distribution and composition of litter and its interactions with fauna were evaluated in the upper S. Vicente canyon using video images from 3 remote operated vehicle exploratory dives. Litter was present in all dives and the abundance was as high as 3.31 items100m(-1). Mean abundance of litter over rock bottom was higher than on soft substrate. Mean litter abundance was slightly higher than reported for other canyons on the Portuguese margin, but lower in comparison to more urbanized coastal areas of the world. Lost fishing gear was the prevalent type of litter, indicating that the majority of litter originates from maritime sources, mainly fishing activity. Physical contact with sessile fauna and entanglement of specimens were the major impacts of lost fishing gear. Based on the importance of this region for the local fishermen, litter abundance is expected to increase.