Contamination of sediments in the floodplain wetlands of the lower uMngeni River,Kwa-Zulu Natal,South Africa

This study describes the geochemical and physico-chemical characterization of contaminant status of six wetlands of the lower uMngeni River floodplain, KwaZulu-Natal Province, South Africa. At all sites, organic matter content, calcium carbonate and metal concentrations were highest within the fine-sediment dominated surface laminae, decreasing with depth. Exceptions were displayed by arsenic (As), nickel (Ni) and vanadium (V), presumed to be derived from normal geochemical processes. Geochemical indicies indicated high contamination factors for lead (Pb) and V, pointing to moderate anthropogenic metal pollution contribution. Most conspicuous are the contamination high factors for Pb across most sites. Fe and Pb contamination is ubiquitous in all surface laminae, with contamination factors being either border-line, moderate or of high contamination. Enrichment factors for As, Mn and P at site S6 indicate possible anthropogenic sources. The data also shows a possibility of anthropogenic input of P and Zn at site S3. Apart from the enrichment factors established for Ni across all sites, all other metals indicate some degree of enrichment. A range of variable results for the mid to deeper laminae are indicative of natural processes with some human influence. Results of ANOVA confirm the above. Principal component analysis reveals a 46.4% variance from component 1 elements (Al, Ca, Cr, Cu, Fe, Mg, Mn and Zn) and a 17.8% variance from component 2 (Al, Cu and Fe). Given the rapid rate of development in this region, the protection of these floodplain wetlands must receive high conservation priority from the local municipality.     

Constraining pathways of microbial mediation for carbonate concretions of the Miocene Monterey Formation using carbonate-associated sulfate

Carbonate concretions can form as a result of organic matter degradation within sediments. However, the ability to determine specific processes and timing relationships to particular concretions has remained elusive. Previously employed proxies (e.g., carbon and oxygen isotopes) cannot uniquely distinguish among diagenetic alkalinity sources generated by microbial oxidation of organic matter using oxygen, nitrate, metal oxides, and sulfate as electron acceptors, in addition to degradation by thermal decarboxylation. Here, we employ concentrations of carbonate-associated sulfate (CAS) and δ³⁴S_CAS (along with more traditional approaches) to determine the specific nature of concretion authigenesis within the Miocene Monterey Formation.Integrated geochemical analyses reveal that at least three specific organo-diagenetic reaction pathways can be tied to concretion formation and that these reactions are largely sample-site specific. One calcitic concretion from the Phosphatic Shale Member at Naples Beach yields δ³⁴S_CAS values near Miocene seawater sulfate (～+22‰ VCDT), abundant CAS (ca. 1000 ppm), depleted δ¹³C_carb (～?11‰ VPDB), and very low concentrations of Fe (ca. 700 ppm) and Mn (ca. 15 ppm)—characteristics most consistent with shallow formation in association with organic matter degradation by nitrate, iron-oxides and/or minor sulfate reduction. Cemented concretionary layers of the Phosphatic Shale Member at Shell Beach display elevated δ³⁴S_CAS (up to ～+37‰), CAS concentrations of ～600 ppm, mildly depleted δ¹³C_carb (～?6‰), moderate amounts of Mn (ca. 250 ppm), and relatively low Fe (ca. 1700 ppm), indicative of formation in sediments dominated by sulfate reduction. Finally, concretions within a siliceous host at Montaña de Oro and Naples Beach show minimal CAS concentrations, positive δ¹³C values, and the highest concentrations of Fe (ca. 11,300 ppm) and Mn (ca. 440 ppm), consistent with formation in sediments experiencing methanogenesis in a highly reducing environment. This study highlights the promise in combining CAS analysis with more traditional techniques to differentiate among diagenetic reactions as preserved in the geologic record and shows potential for unraveling subsurface biospheric processes in ancient samples with a high degree of specificity.     

“You know you can do this,right?”: developing geospatial technological pedagogical content knowledge and enhancing teachers’ cartographic practices with socio-environmental science investigations

Many barriers exist to K–12 classroom teachers’ adoption and implementation of geospatial technologies with their students. To address this circumstance, we have developed and implemented a geospatial curriculum approach to promote teachers’ professional growth with curriculum-linked professional development (PD) to support the adoption of socio-environmental science investigations (SESI) in an urban school environment that includes reluctant learners. SESI focus on social issues related to environmental science. The pedagogy is inquiry-driven, with students engaged in map-based mobile data collection and subsequent analysis with Web-based dynamic mapping software to answer open-ended questions. Working with four science and social studies teachers, we designed and implemented a sequence of three locally oriented, geospatial inquiry projects that were implemented with 140 9th grade students. We investigated how the geospatial curriculum approach impacted the teachers’ geospatial pedagogical content knowledge (PCK), their cartographic practices, and promoted geospatial thinking and analysis skills with their students. Findings revealed strong growth in teachers’ geospatial PCK, increased map use by teachers, use of maps as media for inquiry and not didactic instruction, and modeling to guide students’ geospatial analysis using GIS. Implications for PD to promote teachers’ geospatial PCK and in-class cartographic practices are discussed.     

Clearcutting and pine planting effects on nutrient concentrations and export in two mixed use headwater streams: Upper Coastal Plain,Southeastern USA

Timber harvest temporarily increases water yield; however, relationships between hydrologic and nutrient chemistry changes have not been consistent. This study quantified the effects of forest harvesting and site preparation without fertilization and with modern best management practices on nutrient concentrations and yields in small headwater streams of the Southeastern Coastal Plain. We monitored two watershed pairs for 2 years prior to and 1 year following timber harvest and for 2 more years following site preparation and planting. Treatment watersheds were clearcut, and downstream portions of streamside management zones were thinned in Fall 2003. Site preparation (herbicide application and burning) and planting followed a year later. All operations followed 1999 Georgia forestry best management practices. Previously published research revealed a large increase in water yield following harvest. Nutrient concentrations varied significantly within and between monitoring periods, even in reference watersheds. Silvicultural activities had no discernible effect on phosphorus and ammonium concentrations; however, statistically significant increases in nitrate/nitrite (67–340 µg L⁻¹) and total nitrogen concentrations (100–400 µg L⁻¹) in treatment watersheds followed stand re‐establishment. Nutrient yields increased after timber harvest largely as a result of increased water yields, although increased nutrient yields were small relative to inter‐annual and inter‐watershed variability and variability. Annual water yield largely explained the variability in annual nitrogen and phosphorus export from reference and treatment streams (r² values from 0.65 to 0.98). High NO_x concentrations coming from an upstream agricultural area decreased 1600–1800 µg L⁻¹ over several hundred metres in the treatment streams by dilution, uptake or denitrification. Copyright © 2013 John Wiley & Sons, Ltd.     

Use of Regenerated Scales and Scale Marginal Increments as Indicators of Recent Dietary History in Fish

The potential of teleost scales as indicator tissues of recent dietary history was investigated in the estuarine fish, Notolabrus celidotus. Treatment fish were fed a ¹⁵N-enriched bivalve diet (δ¹⁵N = 108.8‰) for up to 90 days to examine integration of the dietary source signature in scale margin, regenerated scale, and dorsal muscle tissues. Regenerated scales exhibited the greatest and most rapid enrichment in δ¹⁵N (to 53.4 ± 5.0‰) of the tissues examined. Scale margin δ¹⁵N signatures also increased significantly from 14.5‰ to 30.9 ± 6.0‰, while muscle tissue only increased by 2.8‰ after 90 days. Dietary contribution models suggested that isotopic equilibration of dietary nitrogen would be most rapid in regenerated scales, followed by scale marginal increments and then muscle. In conclusion, teleost scales hold considerable potential as novel, nondestructive indicators of recent dietary history, yet currently face constraints from uncertainties in isotopic integration mechanisms.     

GeoNat v1.0: A dataset for natural feature mapping with artificial intelligence and supervised learning

Machine learning allows “the machine” to deduce the complex and sometimes unrecognized rules governing spatial systems, particularly topographic mapping, by exposing it to the end product. Often, the obstacle to this approach is the acquisition of many good and labeled training examples of the desired result. Such is the case with most types of natural features. To address such limitations, this research introduces GeoNat v1.0, a natural feature dataset, used to support artificial intelligence‐based mapping and automated detection of natural features under a supervised learning paradigm. The dataset was created by randomly selecting points from the U.S. Geological Survey’s Geographic Names Information System and includes approximately 200 examples each of 10 classes of natural features. Resulting data were tested in an object‐detection problem using a region‐based convolutional neural network. The object‐detection tests resulted in a 62% mean average precision as baseline results. Major challenges in developing training data in the geospatial domain, such as scale and geographical representativeness, are addressed in this article. We hope that the resulting dataset will be useful for a variety of applications and shed light on training data collection and labeling in the geospatial artificial intelligence domain.     

Southern Ocean biogeochemical impact on the tropical ocean: Stable isotope records from the Pacific for the past 25,000 years

Modeling of oceanic nutrient fields indicates that the Southern Ocean may have a strong impact on the chemistry of the thermocline waters which upwell in the eastern tropical oceans and feed biological productivity there. The subantarctic is a primary source of equatorial undercurrent (EUC) waters. The Southern Ocean to equator connection has been shown through modeling to have a potential influence on atmospheric carbon dioxide content via an increase in the efficiency of the tropical biotic pump (silica leakage hypothesis). On the glacial–interglacial timescale the eastern equatorial Pacific (EEP) has a thermocline (EUC) carbon isotope record which is consistent with that idea and a stronger ice age biologic drawdown in the subantarctic. This carbon isotope record features glacial values more positive than those of the Holocene, which is the reverse of what is seen in the non-equatorial, stratified, ocean. We report planktonic carbon isotope records from the Pacific subantarctic in an effort to trace the unique EEP carbon isotope signature to its source. Our results are compatible with the subantarctic as a source of the tropical carbon isotope signature. Analysis of the glacial to Holocene isotopic pattern in terms of causative process indicates that an increased glacial subantarctic biotic pump accounts best for our observations. This supports the hypothesis of Southern Ocean drive on tropical biological production, and potential impact on the global carbon cycle.     

Synergistic effect of calcium and bicarbonate in enhancing arsenate release from ferrihydrite

Many groundwater systems contain anomalously high arsenic concentrations, associated with less than expected retention of As by adsorption to iron (hydr)oxides. Although carbonates are ubiquitous in aquifers, their relationship to arsenate mobilization is not well characterized. This research examines arsenate release from poorly crystalline iron hydroxides in abiotic systems containing calcium and magnesium with bicarbonate under conditions of static and dynamic flow (pH 7.5-8). Aqueous arsenic levels remained low when arsenate-bearing ferrihydrite was equilibrated with artificial groundwater solution containing Ca, Mg, and HCO₃⁻. In batch titrations in which a solution of Ca and HCO₃⁻ was added repeatedly, the ferrihydrite surface became saturated with adsorbed Ca and HCO₃⁻, and aqueous As levels increased by 1-2 orders of magnitude. In columns containing Ca or Mg and HCO₃⁻, As solubility initially mimicked titrations, but then rapidly increased by an additional order of magnitude (reaching 12 μM As). Separately, calcium chloride and other simple salts did not induce As release, although sodium bicarbonate and lactate facilitated minor As release under flow. Results indicate that adsorption of calcium or magnesium with bicarbonate leads to As desorption from ferrihydrite, to a degree greater than expected from competitive effects alone, especially under dynamic flow. This desorption may be an important mechanism of As mobilization in As-impacted, circumneutral aquifers, especially those undergoing rapid mineralization of organic matter, which induces calcite dissolution and the production of dissolved calcium and bicarbonate.     

The use of regional and alluvial groundwater by riparian trees in the wet-dry tropics of northern Australia

Riparian trees play a critical role in the ecological function of rivers, yet are threatened by anthropogenic change to the hydrological cycle. Identifying the sources of water used by riparian trees can inform sustainable water policy. We used isotopic analysis complemented by measurements of plant water relations to assess water sources for riparian trees at two sites with contrasting hydrogeological processes; one with an alluvial aquifer overlaying an aquitard, and one where fault-induced preferential pathways in the aquitard allowed the flow of deeper, older groundwater from a regional aquifer to the alluvium. At both sites, plant water potential, stomatal conductance, and plant water isotope composition in the xylem sap of riparian trees were collected from two landscape positions, the riverbank and floodplain. We used a Bayesian mixing model (MixSIAR) to assess differences in the proportion of water sources for sites and landscape positions. We found that xylem water isotope values differed between the two sites in line with their hydrogeological characteristics, with trees at the regional aquifer site using water sourced from the regional groundwater and trees at the site with only an alluvial aquifer present using a mixture of water sources, with no dominant source identified. Higher plant predawn water potential values at the regional site indicated greater water availability and support the inference that plants were using more groundwater at the regional site compared to the alluvial site. Trees closer to the river had higher isotope values, indicative of surficial water sources i.e. shallow soil water and river water. Our findings show that the water sources used by riparian trees reflect local hydrogeology and resource availability. Water managers should identify and protect plant water sources to ensure maintenance of riparian trees.     

Thallium Mass Fraction and Stable Isotope Ratios of Sixteen Geological Reference Materials

Thallium stable isotope ratio and mass fraction measurements were performed on sixteen geological reference materials spanning three orders of magnitude in thallium mass fraction, including both whole rock and partially separated mineral powders. For stable isotope ratio measurements, a minimum of three independent digestions of each reference material was obtained. High‐precision trace element measurements (including Tl) were also performed for the majority of these RMs. The range of Tl mass fractions represented is 10 ng g^?1 to 16 μg g^?1, and Tl stable isotope ratios (reported for historical reasons as ε²⁰⁵Tl relative to NIST SRM 997) span the range ?4 to +2. With the exception – attributed to between‐bottle heterogeneity – of G‐2, the majority of data are in good agreement with published or certified values, where available. The precision of mean of independent measurement results between independent dissolutions suggests that, for the majority of materials analysed, a minimum digested mass of 100 mg is recommended to mitigate the impact of small‐scale powder heterogeneity. Of the sixteen materials analysed, we therefore recommend for use as Tl reference materials the USGS materials BCR‐2, COQ‐1, GSP‐2 and STM‐1; CRPG materials AL‐I, AN‐G, FK‐N, ISH‐G, MDO‐G, Mica‐Fe, Mica‐Mg and UB‐N; NIST SRM 607 and OREAS14P.