Simultaneous quantification of dissolved organic carbon fractions and copper complexation using solid-phase extraction

Trace metal cycling in natural waters is highly influenced by the amount and type of dissolved organic C (DOC). Although determining individual species of DOC is unrealistic, there has been success in classifying DOC by determining operationally defined fractions. However, current fractionation schemes do not allow for the simultaneous quantification of associated trace metals. Using operational classifications, a scheme was developed to fractionate DOC based on a set of seven solid-phase extraction (SPE) cartridges. The cartridges isolated fractions based on a range of specific mechanisms thought to be responsible for DOC aggregation in solution, as well as molecular weight. The method was evaluated to determine if it can identify differences in DOC characteristics, including differences in Cu–DOC complexation. Results are that: (1) cartridge blanks were low for both DOC and Cu, (2) differences are observed in the distribution of DOC amongst the fractions from various sources that are consistent with what is known about the DOC materials and the mechanisms operative for each cartridge, (3) when present as a free cation, Cu was not retained by non-cationic cartridges allowing the method to be used to assess Cu binding, (4) the capability of the method to provide quantitative assessment of Cu–DOC complexation was demonstrated for a variety of DOC standards, (5) Cu was found to preferentially bind with high molecular weight fractions of DOC, and (6) estimated partitioning coefficients and conditional binding constants for Cu were similar to those reported elsewhere. The method developed describes DOC characteristics based on specific bonding mechanisms (hydrogen, donor–acceptor, London dispersion, and ionic bonding) while simultaneously quantifying Cu–DOC complexation. The method provides researchers a means of describing not only the extent of DOC complexation but also how that complex will be behave in natural waters.     

Mapping block-and-ash flow hazards based on Titan 2D simulations: a case study from Mt. Taranaki,NZ

Numerical models for simulation of mass flows are typically focussed upon accurately predicting the paths, travel times and inundation from a single flow or collapse event. When considering catchment-based hazards from a volcano, this is complicated by often being faced with several possible scenarios. Over the last 800 years at Mt. Taranaki/Egmont, a number of dome growth and collapse events have resulted in the genesis and emplacement of block-and-ash flows (BAFs). Each BAF was directed northwestward by a breach in the crater rim. The latest dome collapse events in the AD 1880s and AD 1755 inundated the northwestern flank and had run-out lengths 10 km from source. Future activity of this type could have a devastating effect on the Taranaki region’s communities, infrastructure and economy. Hazard planning has involved constructing volcanic hazard maps based upon the areas inundated by past volcanic flows, with little consideration of present-day topography. Here, a numerical geophysical mass flow modelling approach is used to forecast the hazards of future comparable BAF events on NW Mt. Taranaki. The Titan2D programme encompasses a “shallow water”, continuum solution-based, granular flow model. Flow mechanical properties needed for this approach include estimates of internal and basal friction as well as the physical dimensions of the initial collapse. Before this model can be applied to Taranaki BAFs, the input parameters must be calibrated by simulating a range of past collapse events. By using AD 1860 and AD 1755 scenarios, initial collapse volumes can be well constrained and internal and basal friction angles can be evaluated through an iterative approach from previous run-out lengths. A range of possible input parameters was, therefore, determined to produce a suite of potentially inundated areas under present-day terrain. A suite of 10 forecasts from a uniformly distributed range were combined to create a map of relative probabilities of inundation by future BAF events. These results were combined in a GIS package to produce hazard zones related to user-specified hazard thresholds. Using these input parameter constraints, future hazard forecasts for this scale and type of event can also take into account changing summit and topographic configurations following future eruptive or collapse events.     

Phosphorus Speciation in Stream Bed Sediments from an Agricultural Watershed: Solid-Phase Associations and Sorption Behavior

The sorption behavior and solid-phase associations of phosphorus (P) in fine-grained sediments (<63 μm) from two upstream tributaries and one downstream main stem site of the Spoon River in west-central Illinois were characterized to better understand phosphorus bioavailability in this agriculturally dominated watershed. The P sorption affinities, as indicated by linear distribution coefficients (K _d), of all sediments were 330–5,150 L/kg, and negatively correlated with equilibrium phosphorus concentration (EPC_o) values, which ranged between 0.2 and 2.2 μM. pH values measured at the conclusion of the sorption experiments varied only slightly (7.45–8.10) but were nonetheless strongly positively correlated to EPC_o values, and negatively correlated to K _d values, suggesting the importance of pH to the observed sorption behavior. K _d values were generally lower and EPC_o values higher at the main stem site than at the upstream tributary sites, suggesting dissolved reactive P (DRP) bioavailability (specifically orthophosphate) increased downstream. The solid phase associations of P were operationally assessed with the streamlined SEDEX (sedimentary extraction) procedure, and most sediment P (≥50%) was released during the step designed to determine iron oxide–associated P. On average, 70–90% of the total sediment P pool was potentially bioavailable, as estimated by the sum of the iron oxide-, authigenic carbonate-, and organic-associated P fractions. Considerable calcium was also extracted from some sediments during the step designed to specifically remove iron oxide–associated P. It is hypothesized that the severe drought conditions that persisted between April and October, 2005 allowed authigenic carbonates (perhaps partly amorphous) to accumulate, and that these carbonates dissolved during the iron oxide extraction step. The extensive benthic algal populations also present may have aided carbonate precipitation, which under more normal hydrologic conditions would be periodically flushed downstream and replaced by fresh sediment. This suggests antecedent hydrologic conditions played a dominant role in the P sorption and solid phase associations identified.     

Nitrogen Uptake by Native and Invasive Temperate Coastal Macrophytes: Importance of Dissolved Organic Nitrogen

We investigated if the success of the invasive common reed Phragmites australis could be attributed to a competitive ability to use dissolved organic nitrogen (DON) when compared to the dominant macrophyte Spartina alterniflora in tidal wetlands. Short-term nutrient uptake experiments were performed in the laboratory on two genetic lineages of Phragmites (native and introduced to North America) and S. alterniflora. Our results provide the first evidence for direct assimilation of DON by temperate marsh plants and indicate that amino acids are assimilated intact by all plant types at similar rates. Both Phragmites lineages had significantly greater urea–N assimilation rates than S. alterniflora, and the affinity for dissolved inorganic nitrogen (DIN) species was the greatest in native Phragmites > introduced Phragmites > S. alterniflora. Field studies demonstrated uptake of both DON and DIN in similar proportion as those determined in the laboratory experiments. Based on these uptake rates, we estimate that DON has the potential to account for up to 47% of N demand for Phragmites plants, and up to 24% for S. alterniflora plants. Additionally, we suggest that differences in N uptake between native and introduced Phragmites lineages explain one mechanism for the success of the introduced type under increasingly eutrophic conditions.     

Phosphorus Burial in Sediments Along the Salinity Gradient of the Patuxent River,a Subestuary of the Chesapeake Bay (USA)

We used a sequential extraction technique and ²¹⁰Pb dating to determine the chemical form and amount of particulate phosphorus (PP) that is retained during burial in 1-m-long sediment cores collected along a salinity gradient from tidal freshwater to the mesohaline waters of the Patuxent River, a subestuary of the Chesapeake Bay. PP buried in the study sites with salinity values ≤3 was similar in concentration and form to PP entering the Patuxent from the watershed, suggesting efficient sequestration by the sediments at these low-salinity sites. PP extracted with citrate–dithionite–bicarbonate was the dominant form of PP at all salinities and all depths, and organic-P was the second most abundant fraction. We estimated that 81% of PP entering from the watershed is trapped in the sediments of the upper Patuxent subestuary and that the subtidal sediments retain three times as much PP as the marshes adjacent to the study sites.     

Géomorphologie de Tromelin,océan Indien

Tromelin is a small coral reef island (1 km²) located in the Indian Ocean, approximately 440 km east of Madagascar and 580 km north of La Réunion. Despite the presence of a permanent Météo France weather station on Tromelin since the 1950 s, a detailed geomorhological study of the island has never been undertaken. In this paper, we describe results from the 2008 field season, which enabled us to map and describe seven geomorphological zones on the atoll. (1) Tromelin's bathymetry is characterised by a pronounced submarine slope, which attains depths of 1000 m at only 2.5 km from the island's coastline. This geomorphology is typical of volcanic hotspots. (2) A coral platform borders the emerged crown of the island. This platform is exposed at low tide and has been fashioned in an ancient Pleistocene substratum. The substratum has been eroded by abrasive marine action to its present shape since the stabilisation of relative sea level around 6000 years ago. Erosion of the reef yields most of the biogenic sediment supply to the island. (3) The upper foreshore is characterised by outcrops of beachrock. These formations show a stratfication in slabs and dip gently towards the sea in the same manner as the contemporary clastic sediments. (4) Tromelin's beaches are divided into three sub-units, which reflect the different energy dynamics around the island, in addition to the transfer of sediment from the windward to the leeward side: (i) the southern storm beaches are characterised by coral blocks reworked during episodic high-energy events; they form boulder ramparts. Four perched rampart ridges have been recorded at ∼1 m, ∼3 m, ∼4.5 m and ∼7 m above mean sea level; (ii) transitional beaches are observed between the south and the north, constituting storm blocks and coarse sands and gravels; and (iii) sandy beaches are noted on the northern leeward side, comprising rounded gravels and coarse sands. The northern tip of the island is characterised by a sand spit (∼125 × ∼225 m), whose geometry varies based on the seasonal and meteo-marine contexts. (5) On Tromelin, a number of dune formations are observed. These are best developed in the north of the island due to the south-north translation of clastic sediments by aeolian wind action, and the trapping of sands by the well-developed vegetation. The height of the dunes varies between 10 cm (the southern micro-dunes) to 250 cm in the Northeast of Tromelin. (6) Exceptional waves have deposited storm tracts up to 250 m from the foreshore zone, comprising coarse gravels and coral blocks. The storm tract deposits are most prevalent on the windward side of the island, due not only to the high-energy dynamics, but also to the absence of vegetation cover in this area. (7) The southern depression covers an area of ∼40,000 m². At its lowest point it is only 1.2 m above sea level.     

Long-Term Observations of Isotope Ratio Accuracy and Reproducibility Using Quadrupole ICP-MS

High precision isotope ratio and trace element determination can be achieved with modern quadrupole ICP-MS provided that short and long-term instrument performance is accurately monitored. Here we present results for the isotope ratios ⁶Li/⁷Li, ¹⁴⁷Sm/¹⁴⁹Sm, ¹⁶⁰Dy/¹⁶¹Dy, ²⁰⁷Pb/²⁰⁶Pb, ²⁰⁸Pb/²⁰⁶Pb, ²⁰⁶Pb/²⁰⁴Pb and ²³⁵U/²³⁸U with which we determined long-term isotope ratio stability of relevance to both trace element and isotope determination. With respect to trace element determination, we first present long-term observations regarding oxide formation rates of Ba and Nd on light REE and heavy REE, as well as Zr on Ag. These showed good correlations and could be used to correct effectively the interference. The efficacy of this correction was demonstrated with analyses of the rock reference material BHVO-2 at both low and high oxide formation rates. Next, we studied the long-term reproducibility of a Dy isotope ratio that was measured to correct for the isobaric interference on Gd. It was found that, regardless of tuning condition, the ratio reproduced very well (0.58% RSD, 1s) and that the estimate of the Gd concentration did not suffer from the large correction (> 10%) caused by the Dy isobar. Long-term reproducibilities of Li, Sm and U isotope ratios, required for accurate mass bias correction when isotopically enriched internal standards of these elements are employed, were measured in the rock reference materials AGV-2 and JA-3 over a time period of up to 3 years. As expected, the Li isotope ratio showed the largest variability (RSD = 7%), but the other two ratios had relative external reproducibilities of only 1.01% (1s, U) and 0.67% (Sm). The mass bias-induced scatter in measurements for Sm and U was so small that the internal standard correction was effective, even for samples with high concentrations of these elements. With regard to Pb-isotope ratio determination, we also present long-term reproducibility for NIST SRM 982, run as an unknown and two accuracy tests for Pb separated from granitoids and from meteorites. It is demonstrated that the obtained ratios, including those involving ²⁰⁴Pb, are accurate relative to MC-ICP-MS determinations and of comparable precision to conventional TIMS analysis. The excellent agreement between all data sets shows the potential of modern quadrupole ICP-MS instrumentation for Pb-isotope determination, particularly for samples with very low Pb content.     

Mechanism and geochemical implications of the Late Holocene organic carbon burial event: an example from the southwest coast of India

Carbonaceous clay found in the palaeo-deposits of Meenachil River basin was analysed for the total organic carbon, nitrogen and textural characters. Radiocarbon dating of this clay formation and the embedded carbonized wood fragments was also done. The values obtained for the organic carbon, nitrogen and C/N ratio of the carbonaceous clay exhibited a very remarkable range, suggestive of different environmental conditions of formation. It is evident from the present study that since the lignin and cellulose are the dominant components of terrestrial higher plants, allochthonous and submerged organic matter have high C/N ratio. The radio carbon dating of the sediment and wood samples suggested that the palaeo-deposits of Meenachil River basin were formed as result of many transgrassive–regressive episodes, which had started even before the formation of Vembanad Lake. The formation of carbonaceous clay, as found sandwiched in palaeo-deposits, was due to the global eustatic sea-level fluctuations and tectonism.