Organic carbon deposition and phosphorus accumulation during Oceanic Anoxic Event 2 in Tarfaya, Morocco

With a multi-proxy approach, an attempt was made to constrain productivity and bottom-water redox conditions and their effects on the phosphorus accumulation rate at the Mohammed Plage section on the Tarfaya coast, Morocco, during the Cenomanian-Turonian Anoxic Event (OAE 2). A distinct δ¹³C_org isotope excursion of +2.5‰ occurs close to the top of the section. The unusually abrupt shift of the isotope excursion and disappearance of several planktonic foraminiferal species (e.g. Rotalipora cushmani and Rotalipora greenhornensis) in this level suggests a hiatus of between 40–60 kyrs at the excursion onset. Nevertheless, it was possible to determine both the long-term environmental history as well as the processes that took place immediately prior to and during OAE 2. TOC% values increase gradually from the base of the section to the top (from 2.5% to 10%). This is interpreted as the consequence of a long-term eustatic sea-level rise and subsidence causing the encroachment of less oxic waters into the Tarfaya Basin. Similarly a reduction in the mineralogically constructed ‘detrital index’ can be explained by the decrease in the continental flux of terrigenous material due to a relative sea-level rise. A speciation of phosphorus in the upper part of the section, which spans the start and mid-stages of OAE 2, shows overall higher abundances of P_reactive mass accumulation rates before the isotope excursion onset and lower values during the plateau. Due to the probable short hiatus, the onset of the decrease in phosphorus content relative to the isotope excursion is uncertain, although the excursion plateau already contains lower concentrations. The C_org/P_total and V/Al ratios suggest that this reduction was mostly likely caused by a decrease in the available bottom oxygen content (probably as a result of higher productivity) and a corresponding fall in the phosphorus retention ability of the sediment. Productivity appears to have remained high during the isotope plateau possibly due to a combination of ocean-surface fertilisation via increased aridity (increased K/Al and Ti/Al ratios) and/or higher dissolved inorganic phosphorus content in the water column as a result of the decrease in sediment P retention. The evidence for decreased P-burial has been observed in many other palaeoenvironments during OAE 2. Tarfaya's unique upwelling paleosituation provides strong evidence that the nutrient recycling was a global phenomenon and therefore a critical factor in starting and sustaining OAE 2.     

Origin and mechanisms of K–Si-metasomatism of ca. 3.4–3.3 Ga volcaniclastic deposits and implications for Archean seawater evolution: Examples from cherts of Kittys Gap (Pilbara craton, Australia) and Msauli (Barberton Greenstone Belt, South Africa)

The effects of K–Si-metasomatism during the formation of Early Archean replacement cherts have been quantified in this study by the investigation of two well-known stratigraphic sections: the Msauli chert (MC, Barberton greenstone belt, South Africa) and the Kittys Gap chert (KGC, Pilbara craton, Western Australia). The KGCs have a dacitic precursor similar to Duffer Formation dacites (Pilbara craton), while the MCs are derived from Al-depleted komatiites similar to those from the Weltevreden Formation (Barberton greenstone belt). Mass balance calculations reveal that the volcaniclastic deposits had initial porosities of up to 85 vol.% for the KGC and of 65 vol.% for the MC. Secondary porosities (27 vol.%: MC, 8 vol.%: KGC) produced during K-metasomatism are proportional to the dissolution of Fe, Ca, Mg-rich glass and precursor minerals. Komatiites have a higher chemical exchange potential than dacites, each gram releasing 1.2 mmol Fe²⁺, 2.8 mmol Mg²⁺, 1.4 mmol Ca²⁺ and 1.1 mmol Na⁺ to seawater, together with 4.4 mmol O²⁻. K-metasomatism of 1 g of komatiite further implies an uptake of 0.67 mmol of K⁺ and 2.7 mmol of H⁺. The highest silica uptake is achieved for the KGC (82 mmol/g of precursor). This silica enrichment most likely operated in the water column and at the sediment–water interface by sorption mechanisms on the surface of detrital particles and particulate organic matter, as a result of seawater silica-saturation. Acidic conditions (pH 5.5–6.5) and hot temperatures (>70 °C) favored the formation of K-rich phyllosilicates by interaction with seawater during the early diagenetic alteration of the volcaniclastic particles. The widespread occurrence of K–Si-metasomatism in volcanic and sedimentary rocks can be regarded as a general alteration process of the Early Archean seafloor, with a major influence on seawater composition. The highly K-selective metasomatism confirms previous studies suggesting that the Archean ocean was acidic and probably in equilibrium with a CO₂-rich atmosphere.     

Impact evaluation on groundwater of the infiltration of an urban wastewater geopurification system placed over a detrital aquifer in a semiarid region (Spain)

Over a period of 4 years and 4 months, the geopurification installations at Dehesas de Guadix (Granada, Spain) were monitored to determine the impact on soil and groundwater of the controlled discharge of urban wastewater, and also to identify the best indicators of the entry of the recharged water into the aquifer. The installations are located in an area where the climate is Mediterranean sub-arid, with an average precipitation of less than 287 mm/year, and a rate of evapotranspiration that is almost three times greater. The system was controlled by determining the balance of majority nutrients and boron in the soil and in the groundwater, both at the points affected directly by the wastewater discharge and at others. The quantity of mass discharged was relatively large (COD 14,656 g/m², NO₃ 85 g/m², NO₂ 4 g/m², NH₄ 2,425 g/m², PO₄ 1,143 g/m², K 1,531 g/m², B 63 g/m²). It was observed that the elimination of nutrients within the soil (COD 97.5%, PO₄ 94.4%, K 59.17%, N _total 18.8%, B 12.69%) was very efficient except for the nitrogen, which nevertheless did not reach the groundwater, as it was eliminated at deep levels of the unsaturated zone. Only 12.69% of the boron was removed, and appreciable, increasing amounts of this element did reach the groundwater. Unexpectedly, none of the majority nutrients behaved as a reliable indicator of the impact on groundwater; despite this, the boron and the bicarbonate did clearly reflect the arrival of the recharged water, and are proposed as the best indicators.     

Phosphorus transport in shallow groundwater in peri-urban Kampala, Uganda: results from field and laboratory measurements

To understand Phosphorus (P) sources and transport processes in the subsurface in Bwaise III Parish, Kampala, P attenuation and adsorption capacities of soils were studied in situ and from laboratory measurements. Relationships between sorption parameters and soil matrix properties, rates and mechanism of the adsorption process and soil P fractions were also investigated. P was generally higher in the wet than the dry season, but for both seasons, the maximum was 5 mgP/l. P transport mechanisms appeared to be a combination of adsorption, precipitation, leaching from the soil media and by colloids with the latter two playing an important role in the wet season. The sorption process comprised two phases with the first stage rate constants being about fourfold those of the second stage. The Langmuir isotherm described the sorption data well (R ² ≥ 0.95) with the second soil layer exhibiting the highest sorption maximum (C _max) (average value 0.6 ± 0.17 mgP/gDW). The best prediction of C _max had organic carbon, Ca, available P and soil pH. Residual P consisting mostly of organics was the main fraction in all the layers followed by inorganic HCl-P and NaOH-P in the top and middle layers, respectively. Loosely bound P (NH₄Cl-P) was the least fraction (<0.4% of total P) in all layers indicating the high binding capacity of P by the soils. The study results suggest that P dynamics is related to Ca, Fe and organic carbon content of the soils.     

Impacts of at-site wastewater disposal systems on the groundwater aquifer in arid regions: case of Sfax City, Southern Tunisia

Groundwater in Sfax City (Tunisia) has been known since the beginning of the century for its deterioration in quality, as a result of wastewater recharge into the aquifer. An average value of 12 × 10⁶ m³ of untreated wastewater reaches the groundwater aquifer each year. This would result not only in a chemical and biological contamination of the groundwater, but also in an increase of the aquifer piezometric level. Quantitative impacts were evaluated by examining the groundwater piezometric level at 57 surface wells and piezometers. The survey showed that, during the last two decades, the groundwater level was ever increasing in the urban area with values reaching 7 m in part; and decreasing in Sidi Abid (agricultural area) with values exceeding −3 m. Groundwater samples for chemical and microbial analysis were collected from 41 wells spread throughout the study area. Results showed significantly elevated levels of sodium, chlorides, nitrates and coliform bacteria all over the urban area. High levels (NO₃: 56–254 mg/l; Na >1,500 mg/l; Coliforms >30/100 ml) can be related to more densely populated areas with a higher density of pit latrine and recharge wells. Alternatively results showed a very variable chemical composition of groundwater, e.g. electrical conductivity ranges from 4,040 to19,620 μs/cm and the dry residual varies between 1.4 and 14 g/l with concentrations increasing downstream. Furthermore a softening of groundwater in Set Ezzit (highly populated sector) was observed.     

Usefulness of geological,mineralogical, chemical and chemometric analytical techniques in exploitation and profitability studies of iron mines and their associated elements

Due to the high number of variables involved in mine profitability studies, it is often very difficult to establish connections among them in order to provide a blend of market saleable quality products. In this sense, analytical chemistry together with chemometry are essential and indispensable disciplines to tackle these studies. The aim of this work was to demonstrate the utility of these disciplines to carry out optimization studies of iron mines. For this purpose, one of the most important iron mines of the Iberian Peninsula was chosen, sited in the mountain range of Sierra Menera, near the location of Ojos Negros (Teruel, Spain). Geological, mineralogical and chemical composition of 148 samples was analyzed, corresponding to different depths of three drill holes (named TE1, TE2 and TE3). In particular, aspects concerning to chemical composition are very important, since the mean contents of certain elements, such as phosphorus, sodium and potassium, should be restricted to the established limits to prevent that companies can drive back the raw material if they do not fulfil the necessary requirements. On the other hand, the large number of analysed samples drove us to use a statistical processing of the data. Among other aspects, it provides a way to find possible connections among a high number of variables and classify samples into compositional groups sharing similar composition, in order to limit the mineralised area and to obtain enough information about the amount of those chemical elements associated to iron ores. Data obtained from all these analytical techniques were in good agreement and provide a methodology that can be of wide interest applied to different geological studies.     

顶空气相色谱法测定海水二甲基硫和浮游植物细胞二甲基硫丙酸的研究

建立了顶空ＧＣ／ＦＰＤ测定海水中二甲基硫（ＤＭＳ）和浮游植物细胞中二甲基硫丙酸（ＤＭＳＰ）的方法，并研究盐度、温度、气液相比ＤＭＳ诸因素对ＤＭＳ顶空灵敏度的影响。该法对ＤＭＳ测定的相对标准偏差均小于６％，平均回收率为１０６％，最低检出限为２０ｎｇ／Ｌ。细胞ＤＭＳＰ先经碱作用转化为ＤＭＳ，在５０℃下作用时间不少于６ｈ，峰高与浓度的双对数线性相关系数大于０．９９。对１９９４年冬、１９９５年夏采自胶州湾     

污水-海水混合过程中磷转移的动力学

模拟研究厦门市污水排海时污水-海水混合过程中磷含量和形态的变化,及其在海水-颗粒物界面交换的动力学过程;提供转移模式,确定转移速率,进行磷的容量校正,为厦门西海域环境容量估算和水质控制提供定量参数和理论依据。     

天然水体中酚的降解动力学

本文报道了天然水体中低浓度酚的降解动力学;计算了它的降解速率常数、降解活化能等。降解半表期是t_(1/2)=1.5d~(-1)(10℃),t_(1/2)=O.74d~(-1)(30℃)。低浓度酚的降解动力学跟天然水体中酚的降解情况比较接近。本文的结果对环境评价、蓄水库工程设计等很有参考价值。     

On the relevance of iron adsorption to container materials in small-volume experiments on iron marine chemistry: Fe-aided assessment of capacity, affinity and kinetics

Iron chemistry in seawater has been extensively studied in the laboratory, mostly in small-volume sample bottles. However, little has been reported about iron wall sorption in these bottles. In this paper, radio-iron ⁵⁵Fe was used to assess iron wall adsorption, both in terms of capacity, affinity and kinetics. Various bottle materials were tested. Iron sorption increased from polyethylene/polycarbonate to polymethylmetacrylate (PMMA)/high-density polyethylene/polytetrafluoroethylene to glass/quartz, reaching equilibrium in a 25–70 h period. PMMA was studied in more detail: ferric iron (Fe(III)) adsorbed on the walls of the bottles, whereas ferrous iron (Fe(II)) did not. Considering that in seawater the inorganic iron pool mostly consists of ferric iron, the wall will be a factor that needs to be considered in bottle experiments.The present data indicate that for PMMA with specific surface (S)-to-volume (V) ratio S/V, both iron capacity (42 ± 16 × 10^− 9 mol/m² or 1.7 × 10^− 9 mol/L recalculated for the S/V-specific PMMA bottles used) and affinity (log K_Fe'W = 11.0 ± 0.3 m²/mol or 12.4 ± 0.3 L/mol, recalculated for the S/V-specific PMMA bottles used) are of similar magnitude as the iron capacity and -affinity of the natural ligands in the presently used seawater and thus cannot be ignored.Calculation of rate constants for association and dissociation of both Fe'L (iron bound to natural occurring organic ligands) and Fe'W (iron adsorbed on the wall of vessels) suggests that the two iron complexes are also of rather similar kinetics, with rate constants for dissociation in the order of 10 ⁻⁴–10^− 5 L/s and rate constants for association in the order of 10⁸ L/(mol s). This makes that iron wall sorption should be seriously considered in small-volume experiments, both in assessments of shorter-term dynamics and in end-point observations in equilibrium conditions. Therefore, the present data strongly advocate making use of iron mass balances throughout in experiments in smaller volume set-ups on marine iron (bio) chemistry.