Multiproxy record for the last 4500 years from Lake Shkodra (Albania/Montenegro)

A multi‐proxy record is presented for approximately the last 4500 cal a BP from Lake Shkodra, Albania/Montenegro. Lithological analyses, C/N ratio and δ¹³C of the organic and inorganic carbon component suggest that organic matter and bulk carbonate are predominantly authigenic. The δ¹⁸O record of bulk carbonate indicates the presence of two prominent wet periods: one at ca. 4300 cal a BP and one at ca. 2500–2000 cal a BP. The latter phase is also found in southern Spain and Central Italy, and represents a prominent event in the western and central Mediterranean. In the last 2000 years, four relatively wet intervals occurred between ca. 1800 and 1500 cal a BP (150–450 AD), 1350–1250 (600–700 AD), 1100–800 (850–1150 AD), and at ca. 90 cal a BP (1860 AD). Between ca. 4100 and 2500 cal a BP δ¹⁸O values are relatively high, with three prominent peaks indicating drier conditions at ca. 4100–4000 cal a BP, ca. 3500 and at ca. 3300 cal a BP. Four additional drier events are identified at 1850 (ca. 100 AD), 1400 (ca. 550 AD), 1150 (800 AD) and ca.750 cal a BP (1200 AD). The pollen record does not show changes in accordance with these episodes owing to the poor sensitivity of vegetation in this area, which is dominated by an orographic rainfall effect and where changes in altitudinal vegetation belts do not affect the pollen rain in the lake catchment. However, since ca. 900 cal a BP a significant decrease in the percentage arboreal pollen and in pollen concentrations suggest major deforestation produced by human activities. Copyright © 2012 John Wiley & Sons, Ltd.     

Multivariate statistical analysis and environmental isotopes of Amman/Wadi Sir (B2/A7) groundwater,Yarmouk River Basin,Jordan

Multivariate statistical techniques, cluster and factor analyses were applied on the Amman/Wadi Sir groundwater chemistry, Yarmouk River basin, north Jordan. The main objective was to investigate the main processes affecting the groundwater chemical quality and its evolution. The k‐means cluster analysis yields three groups with distinct ionic concentrations. Cluster 1 comprises the vast majority of the sampled wells, and the water that belongs to this cluster can be classified as freshwater. Cluster 2 comprises only 2% of the sampled wells; it has the highest ionic concentration. The water of this cluster can be classified as brackish water. Cluster 3 involves 23% of the sampled wells, and it has total ionic concentration intermediate to that of clusters 1 and 2. Factor analysis yields a three‐factor model, which explains 76.77% of the groundwater quality variation. Factor 1 ‘salinity factor’ involves EC, Na⁺, Cl^‐, SO₄^‐2, K⁺ and Mg⁺² and reflects groundwater salinization because of overpumping. Factor 2 ‘hardness factor’ includes Ca⁺², HCO₃^‐ and the pH value and signifies soil–water/rock interaction. Factor 3 ‘nitrate factor’ involves only NO₃^‐ and points to groundwater contamination because of human activities, mainly untreated wastewater, and crops and animal cultivation in the unconfined portion of the aquifer. Factors 1 and 3 can be described as human‐induced factors, whereas factor 2 can be described as geogenic factor. Factors' scores were mapped to deduce the controlling processes on the groundwater chemistry. Stable isotope composition of ¹⁸O and ²H has revealed that the groundwater is a mixture of two water types. The radioactive isotopes tritium and ¹⁴ C were used to evaluate present day recharge to the aquifer and to estimate the groundwater age, respectively. Present day recharge to the groundwater is taking place in the unconfined portion of the aquifer as it is indicated by the measurable tritium content and low groundwater age. Copyright © 2012 John Wiley & Sons, Ltd.     

High‐resolution geochemical record of fluid–rock interaction in a mid‐crustal shear zone: a comparative study of major element and oxygen isotope transport in garnet

Garnet grains from an intensely metasomatized mid‐crustal shear zone in the Reynolds Range, central Australia, exhibit a diverse assortment of textural and compositional characteristics that provide important insights into the geochemical effects of fluid–rock interaction. Electron microprobe X‐ray maps and major element profiles, in situ secondary ion mass spectrometry oxygen isotope analyses, and U–Pb and Sm–Nd geochronology are used to reconstruct their thermal, temporal and fluid evolution. These techniques reveal a detailed sequence of garnet growth, re‐equilibration and dissolution during intracontinental reworking associated with the Ordovician–Carboniferous (450–300 Ma) Alice Springs Orogeny. A euhedral garnet porphyroblast displays bell‐shaped major element profiles diagnostic of prograde growth zoning during shear zone burial. Coexisting granulitic garnet porphyroclasts inherited from precursor wall rocks show extensive cation re‐equilibration assisted by fracturing and fragmentation. Oxygen isotope variations in the former are inversely correlated with the molar proportion of grossular, suggesting that isotopic fractionation is linked to Ca substitution. The latter generally show close correspondence to the isotopic composition of their precursor, indicating slow intergranular diffusion of O relative to Fe²⁺, Mg and Mn. Peak metamorphism associated with shearing (～550 °C; 5.0–6.5 kbar) occurred at c. 360 Ma, followed by rapid exhumation and cooling. Progressive Mn enrichment in rim domains indicates that the retrograde evolution caused partial garnet dissolution. Accompanying intra‐mineral porosity production then stimulated limited oxygen isotope exchange between relict granulitic garnet grains and adjacent metasomatic biotite, resulting in increased garnet δ¹⁸O values over length scales <200 μm. Spatially restricted oxygen interdiffusion was thus facilitated by increased fluid access to reaction interfaces. The concentration of Ca in channelled fracture networks suggests that its mobility was enhanced by a similar mechanism. In contrast, the intergranular diffusion of Fe²⁺, Mg and Mn was rock‐wide under the same P–T regime, as demonstrated by a lack of local spatial variations in the re‐equilibration of these components. The extraction of detailed reaction histories from garnet must therefore take into account the variable length‐ and time‐scales of elemental and isotopic exchange, particularly where the involvement of a fluid phase enhances the possibility of measureable resetting profiles being generated for slowly diffusing components such as Ca and O, even at low ambient temperatures and relatively fast cooling rates.     

A multiproxy record of late Holocene natural and anthropogenic environmental change from the Sphagnum peat bog Dürres Maar,Germany: implications for quantitative climate reconstructions based on pollen

Pollen data are well established for quantitative climate reconstructions over long timescales, including the Holocene and older interglacials. However, anthropogenically induced environmental change in central Europe was strong during the last 4 ka, challenging quantitative reconstructions of this time period. Here we present quantitative climate reconstructions based on pollen analyses and evaluate them with the peat humification record and the stable carbon isotopes of Sphagnum plant material (δ¹³C_cellulose). All analyses were carried out on the same 7.5 m long, largely ombrotrophic peat bog section from Dürres Maar. Three different methods were used for the quantitative climate reconstructions on the basis of the pollen data: (1) a probabilistic indicator taxa approach (the ‘pdf method’); (2) a modern analogue technique based on pollen taxa from modern surface samples (cMAT); and (3) a modern analogue technique expanded by plant functional types (pMAT). At Dürres Maar the peat humification is only affected by peat cutting during the Roman period and the Middle Ages. The stable carbon isotopes are seemingly unaffected by human impact. Thus both proxies provide independent data to evaluate the reconstructions on the basis of pollen data. The quantitative climate reconstructions on the basis of the individual methods are in general relatively similar. Nevertheless, distinct differences between the individual approaches are also apparent, which could be attributed to taxa that reflect human impact on a local to regional scale. While the pdf method appears to be relatively robust to all observed anthropogenically induced vegetation changes, it potentially underestimates climate variability. This method is therefore expected to be independent of local site characteristics and to provide robust quantitative estimates of climatic trends rather than of climatic variability of small amplitude. This is of value for palaeoclimate reconstructions of older interglacials, for which neither multiple sites nor independent climate proxies are available for comparison. Copyright © 2009 John Wiley & Sons, Ltd.     

Identifying surface water evaporation loss of inland river basin based on evaporation enrichment model

Accurately quantifying the evaporation loss of surface water is essential for regional water resources management, especially in arid and semi-arid areas where water resources are already scarce. The long-term monitoring of stable isotopes (δ¹⁸O and δ²H) in water can provide a sensitive indicator of water loss by evaporation. In this study, we obtained surface water samples of Shiyang River Basin from April to October between 2017 and 2019. The spatial and temporal characteristics of stable isotopes in surface water show the trend of enrichment in summer, depletion in spring, enrichment in deserts and depletion in mountains. The Local Evaporation Line (LEL) obtained by the regression of δ²H and δ¹⁸O in surface water has been defined by the lines: δ²H = 7.61δ¹⁸O + 14.58 for mountainous area, δ²H = 4.19δ¹⁸O − 17.85 for oasis area, δ²H = 4.08δ¹⁸O − 18.92 for desert area. The slope of LEL shows a gradual decrease from mountain to desert, indicating that the evaporation of surface water is gradually increasing. The evaporation loss of stable isotopes in surface water is 24.82% for mountainous area, 32.19% for oasis area, and 70.98% for desert area, respectively. Temperature and air humidity are the main meteorological factors affecting the evaporation loss, and the construction of reservoirs and farmland irrigation are the main man-made factors affecting the evaporation loss.     

Sub‐millennial climate shifts in the western Mediterranean during the last glacial period recorded in a speleothem from Mallorca,Spain

Very few high‐resolution and directly dated terrestrial archives of the last glacial period exist for the western Mediterranean region, yet this is a key locality for recording sub‐millennial North Atlantic and Mediterranean climate change. Here, we present evidence of effective precipitation changes based on growth history and δ¹³C of calcite in a Mallorcan stalagmite that grew between 112 and 48 ka. Effective precipitation in Mallorca appears to have been sensitive to proximal sea surface temperature variations and at certain times, ca. 76 ka for example, changed rapidly from moist to arid conditions in only a few centuries. A sea‐level highstand during Marine Isotope Stage (MIS) 5a interrupted growth. Regrowth started promptly after this, but effective precipitation decreased markedly for much of the later part of MIS 5a, and also for shorter periods correlative with Heinrich events H8 (ca. 90 ka) and H6 (ca. 65 ka), with growth ceasing during H5 (ca. 48 ka). Arid episodes in Mallorca appear to be expressions of extremely cold periods recorded further north in Europe and occur contemporaneously with rapid decreases in Greenland temperature. Copyright © 2008 John Wiley & Sons, Ltd.     

Contribution to the study of thermal waters in Greece: chemical patterns and origin of thermal water in the thermal springs of Lesvos

The occurrence of thermal/spa waters on Lesvos Island is related to the presence of a major faulting system. Thermal waters are the result of mixing of meteoric and infiltrating seawater at great depth, and their total salinity depends on the percentage of seawater in their composition. According to the diagrams of main elements, trace elements and environmental isotopes, most of the components that determine the chemical composition of thermal waters such as sodium, chloride and sulphates originate from seawaters. On the other hand, the concentration of calcium, magnesium, boron, lithium, etc., was affected by water–rock interaction under high temperature conditions. Moving towards the surface, thermal waters may become polluted by influx of recent seawater, allowing their chemical composition to become similar to that of seawater. The thermal waters of Lesvos Island present relatively high concentrations of ammonia and redox sensitive metals because they are hosted in a reducing environment. They also exhibit low nitrate concentrations due to their mixture with recent fresh water. Finally, they show increased radon concentrations, ranging from 20 to 60 kBq m^?3 in the eastern and southern parts of the island, and about 230 kBq m^?3 in the north, in the area of Eftalou–Argenos. Copyright © 2007 John Wiley & Sons, Ltd.     

Carbon dioxide,methane, and dissolved carbon dynamics in an urbanized river system

Estimates of greenhouse gas evasion from rivers have been refined over the past decades to constrain their role in global carbon cycle processes. However, despite 55% of the human population living in urban areas, urban rivers have had limited attention. We monitored carbon dynamics in an urbanized river (River Kelvin, 331 km², UK) to explore the drivers of dissolved carbon lateral and vertical export. Over a 2-year sampling period, riverine methane (CH₄) and carbon dioxide (CO₂) concentrations were consistently oversaturated with respect to atmospheric equilibria, leading to continual degassing to the atmosphere. Carbon stable isotopic compositions (δ¹³C) indicated that terrestrially derived carbon comprised most of the riverine CH₄ and dissolved CO₂ (CO₂*) load while dissolved inorganic carbon (DIC) from groundwater was the main form of riverine DIC. The dynamics of CH₄, CO₂*, and DIC in the river were primarily hydrology-controlled, that is, [CH₄] and [CO₂*] both increased with elevated discharge, total [DIC] decreased with elevated discharge while the proportion of biologically derived DIC increased with increasing discharge. The concentration of dissolved organic carbon (DOC) showed a weak relationship with river hydrology in summer and autumn and was likely influenced by the combined sewer overflows. Carbon emission to the atmosphere is estimated to be 3.10 ± 0.61 kg C·m⁻²·yr⁻¹ normalized to water surface area, with more than 99% emitted as CO₂. Annual carbon loss to the coastal estuary is approximately 4.69 ± 0.70 Gg C yr⁻¹, with annual DIC export approximately double that of DOC. Per unit area, the River Kelvin was a smaller carbon source to the atmosphere than natural rivers/streams but shows elevated fluxes of DIC and DOC under comparable conditions. This research illustrates the role urban systems may have on riverine carbon dynamics and demonstrates the potential tight link between urbanization and riverine carbon export.     

Investigating young water fractions in a small Mediterranean mountain catchment: Both precipitation forcing and sampling frequency matter

The proportion of water younger than 2–3 months (young water fraction, F_yw) has become increasingly investigated in catchment hydrology. F_yw is typically estimated by comparing seasonal tracer cycles in precipitation and streamflow, through water sampling. However, some open research questions remain, such as: (i) whether part of the summer precipitation should be discarded because the high evapotranspiration demand, (ii) how well F_yw serves as a metric to compare catchments, and (iii) how sampling frequency affects F_yw estimates. To address these questions, we investigated F_yw in soil-, ground- and stream waters for the small Mediterranean Can Vila catchment. Rainfall was sampled at 5-mm intervals. Mobile soil water and groundwater were sampled fortnightly. Stream water was sampled depending on flow at variable time intervals (30 min to 1 week). Over 58 months, this sampling provided 1,529 δ¹⁸O determinations. Isotopic analyses results led us to include summer precipitation in the input signal. We found the highest F_yw in mobile soil waters (34%), while this was almost zero for groundwater except during wet periods. For stream waters, F_yw depended on the discharge variations, so that the flow-weighted young water fraction () was 22.6%, whereas the time-weighted F_yw was just 6.2%. Both and its discharge sensitivity (S_d) varied when different 12-month sampling periods were investigated. The young water fraction that would be obtained from a virtual thorough sampling () was estimated from the S_d and the observed stream flow. This showed an underestimation of by 25% for the frequent dynamic sampling and 66% for weekly sampling, due to missing high flows. Our results confirm that F_yw and its discharge sensitivity are metrics very sensitive to meteorological forcing during the analysed period. Thus, comparisons between catchments need long-term mean annual values and their variability. Our findings also support the dependence of F_yw estimates on the sampling rate and show the advantages of flow-weighted analysis. Finally, catchment water turnover investigations should be accompanied by the analysis of flow duration curves.