Influence of time on the plant availability of Cd, Ni and Zn after sewage sludge has been applied to soils

A pot experiment was conducted to test the hypothesis that decomposition of organic matter in sewage sludge and the consequent formation of dissolved organic compounds (DOC) would lead to an increase in the bioavailability of the heavy metals. Two Brown Earth soils, one with clayey loam texture (CL) and the other a loamy sand (LS) were mixed with sewage sludge at rates equivalent to 0, 10 and 50 1 dry sludge ha(-1) and the pots were sown with ryegrass (Lolium perenne L.). The organic matter content and heavy metal availability assessed with soil extractions with 0.05 M CaCl2 were monitored over a residual time of two years, while plant uptake over one year, after addition of the sludge. It was found that the concentrations of Cd and Ni in both the ryegrass and the soil extracts increased slightly but significantly during the first year. In most cases, this increase was most evident especially at the higher sludge application rate (50 t ha(-1)). However, in the second year metal availability reached a plateau. Zinc concentrations in the ryegrass did not show an increase but the CaCl2 extracts increased during the first year. In contrast, organic matter content decreased rapidly in the first months of the first year and much more slowly in the second (total decrease of 16%). The concentrations of DOC increased significantly in the more organic rich CL soil in the course of two years. The pattern followed by the decomposition of organic matter with time and the production of DOC may provide at least a partial explanation for trend towards increased metal availability.

Joined-up archaeology at Old Scatness, Shetland: thin section analysis of the site and hinterland

Excavations on the multi-period settlement at Old Scatness, Shetland have uncovered a number of Iron Age structures with compacted, floor-like layers. Thin section analysis was undertaken in order to investigate and compare the characteristics of these layers. The investigation also draws on earlier analyses of the Iron Age agricultural soil around the settlement and the midden deposits that accumulated within the settlement, to create a 'joined-up' analysis which considers the way material from the settlement was used and then recycled as fertiliser for the fields. Peat was collected from the nearby uplands and was used for fuel and possibly also for flooring. It is suggested that organic-rich floors from the structures were periodically removed and the material was spread onto the fields as fertilisers. More organic-rich material may have been used selectively for fertiliser, while the less organic peat ash was allowed to accumulate in middens. Several of the structures may have functioned as byres, which suggests a prehistoric plaggen system.

Weathering microenvironments on feldspar surfaces: implications for understanding fluid-mineral reactions in soils

The mechanisms by which coatings develop on weathered grain surfaces, and their potential impact on rates of fluid-mineral interaction, have been investigated by examining feldspars from a 1.1 ky old soil in the Glen Feshie chronosequence, Scottish highlands. Using the focused ion beam technique, electron-transparent, foils for characterization by transmission electron microscopy were cut from selected parts of grain surfaces. Some parts were bare whereas others had accumulations, a few micrometres thick, of Weathering products, often mixed with mineral and microbial debris. Feldspar exposed at bare grain surfaces is crystalline throughout and so there is no evidence for the presence of the amorphous 'leached layers' that typically form in acid-dissolution experiments and have been described from some natural Weathering contexts. The weathering products comprise sub-mu m thick crystallites of an Fe-K aluminosilicate, probably smectite, that have grown within an amorphous and probably organic-rich matrix. There is also evidence for crystallization of clays having been mediated by fungal hyphae. Coatings formed within Glen Feshie soils after similar to 1.1 ky are insufficiently continuous or impermeable to slow rates Of fluid-feldspar reactions, but provide valuable insights into the complex Weathering microenvironments oil debris and microbe-covered mineral surfaces.

Bridging the Faraoni and Selli oceanic anoxic events: late Hauterivian to early Aptian dysaerobic to anaerobic phases in the Tethys.

A detailed geochemical analysis was performed on the upper part of the Maiolica Formation in the Breggia (southern Switzerland) and Capriolo sections (northern Italy). The analysed sediments consist of well-bedded, partly siliceous, pelagic carbonate, which lodges numerous thin, dark and organic-rich layers. Stable-isotope, phosphorus, organic-carbon and a suite of redox-sensitive trace-element contents (RSTE: Mo, U, Co, V and As) were measured. The RSTE pattern and Corg:Ptot ratios indicate that most organic-rich layers were deposited under dysaerobic rather than anaerobic conditions and that latter conditions were likely restricted to short intervals in the latest Hauterivian, the early Barremian and the pre-Selli early Aptian. Correlations are both possible with organic-rich intervals in central Italy (the Gorgo a Cerbara section) and the Boreal Lower Saxony Basin, as well as with the facies and drowning pattern in the Helvetic segment of the northern Tethyan carbonate platform. Our data and correlations suggest that the latest Hauterivian witnessed the progressive installation of dysaerobic conditions in the Tethys, which went along with the onset in sediment condensation, phosphogenesis and platform drowning on the northern Tethyan margin, and which culminated in the Faraoni anoxic episode. This episode is followed by further episodes of dysaerobic conditions in the Tethys and the Lower Saxony Basin, which became more frequent and progressively stronger in the late early Barremian. Platform drowning persisted and did not halt before the latest early Barremian. The late Barremian witnessed diminishing frequencies and intensities in dysaerobic conditions, which went along with the progressive installation of the Urgonian carbonate platform. Near the Barremian-Aptian boundary, the increasing density in dysaerobic episodes in the Tethyan and Lower Saxony Basins is paralleled by a change towards heterozoan carbonate production on the northern Tethyan shelf. The following return to more oxygenated conditions is correlated with the second phase of Urgonian platform growth and the period immediately preceding and corresponding to the Selli anoxic episode is characterised by renewed platform drowning and the change to heterozoan carbonate production. Changes towards more humid climate conditions were the likely cause for the repetitive installation of dys- to anaerobic conditions in the Tethyan and Boreal basins and the accompanying changes in the evolution of the carbonate platform towards heterozoan carbonate-producing ecosystems and platform drowning.

Progressive palaeoenvironmental change during the Late Barremian-Early Aptian as prelude to Oceanic Anoxic Event 1a: Evidence from the Gorgo a Cerbara section (Umbria-Marche basin, central Italy)

During Oceanic Anoxic Event 1a (OAE 1a, 120 Ma; Li et al., 2008), organic carbon-rich layers were deposited in marine environments under anoxic conditions on a global scale. In this study, palaeoenvironmental conditions leading to this event are characterised by studying the Upper Barremian to the Lower Aptian succession of the Gorgo a Cerbara section (central Italy). For this, an integrated multi-proxy approach (δ13Ccarb; δ13Corg; δ18O; phosphorus; Total Organic Carbon, TOC; bulk-rock mineralogy, as well as redox-sensitive trace elements — RSTEs) has been applied. During the LateBarremian, thin organic-rich layers occur episodically, and associated Corg:Ptot ratios indicate the presence of intermittent dysoxic to anoxic conditions. Coarse correlations are observed between TOC, P and biogenic silica contents, indicating links between P availability, productivity, and TOC preservation. However, the corresponding δ13Ccarb and δ18O records remain quite stable, indicating that these brief periods of enhanced TOC preservation did not have sufficient impact on the marine carbon reservoir to deviate δ13C records. Around the Barremian–Aptian boundary, TOC-enriched layers become more frequent. These layers correlate with negative excursions in the δ13Ccarb and δ13Corg records, possibly due to a warming period as indicated by the δ18O record. During the earliest Aptian, this warming trend is reverted into a cooling trend, which is then followed by an important warming step near the onset of Oceanic Anoxic Event 1a (OAE 1a). During this time period, organic-rich intervals occur, which are characterised by the progressive increase in RSTE. The warming step prior the onset of OAE 1a is associated with the well-known negative spike in δ13Ccarb and δ13Corg records, an important peak in P accumulation, RSTE enrichments and Corg:Ptot ratios indicating the prevalence of anoxic conditions. The Selli Level itself may document a cooling phase. RSTE enrichments and Corg:Ptot ratios confirm the importance of anoxic conditions during OAE 1a at this site. The Gorgo a Cerbara section is interpreted to reflect the progressive impact of palaeoenvironmental change related to the formation of the Ontong-Java plate-basalt plateau, which started already around the Barremian–Aptian boundary and culminated into OAE 1a.

The expression of the end-Cenomanian oceanic anoxic event (OAE 2) in the Helvetic Alps

Upper Cenomanian pelagic sediments from the northern Alpine Helvetic fold-and-thrust belt (northern Tethyan margin) coeval with Oceanic Anoxic Event (OAE) 2 are characterized by the temporal persistence of micrite sedimentation and lack of organic carbon-rich layers. We studied an expanded section in the Chrummflueschlucht (east of Euthal, Switzerland), which encompasses the OAE 2 time interval. In order to identify the paleoceanographic and paleoenvironmental conditions during OAE 2 in this part of the northern Tethyan margin, and more specifically to trace eventual changes in nutrient levels and oxic conditions, we investigated the biostratigraphy (planktonic foraminifera), the bulk-rock mineralogy, and measured stable carbon- and oxygen-isotopes, total phosphorus (P) and redox-sensitive trace-element (RSTE) contents. We were able to determine – with some remaining uncertainties – the different planktonic foraminiferal biozones characteristic of the Cenomanian–Turonian boundary interval (Rotalipora cushmani, Whiteinella archaeocretacea and Helvetoglobotruncana helvetica zones). In the lower part of the section (R. cushmani total range zone), the bulk-rock δ13C record shows a long-term increase. Within sediments attributed to the W. archaeocretacea partial range zone, δ13C values reach a maximum of 3.3‰ (peak “a”). In the following the values decrease and increase again to arrive at a plateau with high δ13C values of around 3.1‰, which ends with a peak of 3.3‰ (peak “c”). At the top of the section, in sediments belonging to the H. helvetica total range zone, δ13C values decrease to post-OAE values of around 2.2‰. The last occurrence of R. cushmani is observed just above the positive δ13C shift characterizing OAE 2. P contents display small variations along the section with a long-term decreasing trend towards the top. Before the OAE 2 interval, P values show higher values and relatively good covariation with detrital input, indicating higher nutrient input before OAE 2. In sediments corresponding to the onset of the δ13C positive excursion, P content is marked by a sharp peak probably linked to a slowdown in sedimentation rates and/or the presence of a small hiatus, as is shown by the presence of glauconite and phosphatic grains. In the interval corresponding to OAE 2, P values remain low and increase slightly at the end of the positive shift in the δ13C record (in the H. helvetica total range zone). The average contents of RSTE (U, V, As, Co, Mo and Mn) remain low throughout the section and appreciable RSTE enrichments have not been observed for the sedimentary interval corresponding to OAE 2. No correlation is observed with stratigraphic trends in RSTE contents in organic-rich deeper-water sections. The presence of double-keeled planktonic foraminifera species during most of the Cenomanian/Turonian boundary event is another evidence of relatively well-oxygenated conditions in this part of the northern Tethyan outer shelf. Our results show that the Chrummflueschlucht section corresponds to one of the most complete section for the Cenomanian–Turonian boundary interval known from the Helvetic realm even if a small hiatus may be present at the onset of the δ13C record (peak “a”). The evolution of P contents suggests an increase in input of this nutritive element at the onset of OAE2. However, the trends in RSTE contents and the planktonic foraminifera assemblages show that the Helvetic realm has not been affected by strongly depleted oxygen conditions during OAE 2.

Nitrogen speciation and phosphorus fractionation dynamics in a lowland chalk catchment

A detailed analysis of temporal and spatial trends in nitrogen (N) speciation and phosphorus (P) fractionation in the Wylye, a lowland Chalk sub-catchment of the Hampshire Avon, UK is presented, identifying the sources contributing to nutrient enrichment, and temporal variability in the fractionation of nutrients in transit from headwaters to lower reaches of the river. Samples were collected weekly from ten monitoring stations with daily sampling at three further sites over one year, and monthly inorganic N and total reactive P (TRP) concentrations at three of the ten weekly monitoring stations over a ten year period are also presented. The data indicate significant daily and seasonal variation in nutrient fractionation in the water column, resulting from plant uptake of dissolved organic and inorganic nutrient fractions in the summer months, increased delivery of both N and P from diffuse sources in the autumn to winter period and during high flow events, and lack of dilution of point source discharges to the Wylye from septic tank, small package Sewage Treatment Works (STW) and urban Waste Water Treatment Works (WwTW) during the summer low flow period. Weekly data show that contributing source areas vary along the river with headwater N and P strongly influenced by diffuse inorganic N and particulate P fluxes, and SRP and organic-rich point source contributions from STW and WwTW having a greater influence in the lower reaches. Long-term data show a decrease in TRP concentrations at all three monitoring stations, with the most pronounced decrease occurring downstream from Warminster WwTW, following the introduction of P stripping at the works in 2001. Inorganic N demonstrates no statistically significant change over the ten year period of record in the rural headwaters, but an increase in the lower reaches downstream from the WwTW which may be due to urban expansion in the lower catchment.

Effects of acid sulphate on DOC release in mineral soils: the influence of SO42−retention and Al release

Dissolved organic carbon (DOC) in acid-sensitive upland waters is dominated by allochthonous inputs from organic-rich soils, yet inter-site variability in soil DOC release to changes in acidity has received scant attention in spite of the reported differences between locations in surface water DOC trends over the last few decades. In a previous paper, we demonstrated that pH-related retention of DOC in O horizon soils was influenced by acid-base status, particularly the exchangeable Al content. In the present paper, we investigate the effect of sulphate additions (0–437 μeq l−1) on DOC release in the mineral B horizon soils from the same locations. Dissolved organic carbon release decreased with declining pH in all soils, although the shape of the pH-DOC relationships differed between locations, reflecting the multiple factors controlling DOC mobility. The release of DOC decreased by 32–91% in the treatment with the largest acid input (437 μeq l−1), with the greatest decreases occurring in soils with very small % base saturation (BS, <3%) and/or large capacity for sulphate (SO42−) retention (up to 35% of added SO42−). The greatest DOC release occurred in the soil with the largest initial base status (12% BS). These results support our earlier conclusions that differences in acid-base status between soils alter the sensitivity of DOC release to similar sulphur deposition declines. However,superimposed on this is the capacity of mineral soils to sorb DOC and SO42−, and more work is needed to determine the fate of sorbed DOC under conditions of increasing pH and decreasing SO42−.

The expression of the Cenomanian-Turonian oceanic anoxic event in Tibet

The Gongzha section of Tibet, China is located at the northern margin of the Indian Plate (SE Tethys) and is characterized by hemipelagic grey marls and marly limestones, light grey limestones and silty limestones, but no organic-rich sediments. High-resolution biostratigraphy reveals an expanded Cenomanian–Turonian (CT) boundary interval and the δ13C record includes the main features of the classical positive carbon-isotope excursion that characterizes the CT oceanic anoxic event. The biotic response inferred from the foraminifera suggests that oxic to dysoxic conditions prevailed, except for a short interval marked by peak abundance of Heterohelix that indicates a significantly dysoxic environment during the δ13C “b” peak excursion. The overall decreasing trend in redox-sensitive trace elements (RSTE) during the maximum δ13C excursion confirms the absence of significant longer-lasting anoxia in the Gongzha section. Enrichments in RSTE are linked to phases of increased detrital input. Chemical weathering indices suggest that the upper Cenomanian sediments accumulated under an increasingly hot and humid climate that culminated near the CT boundary. In the early Turonian lower weathering indices suggest a warm, drier climatic regime with reduced continental runoff. Phosphorus mass-accumulation rates show a significant peak at the onset of the positive δ13C excursion, followed by a decrease up to the basal Turonian. This pattern is positively correlated with the long-term decrease in detrital index as also observed in numerous other CT boundary sections (e.g., Eastbourne, Pueblo, and Whadi El Ghaib, Sinaï). Long-term phosphorus accumulation in the Gongzha section is therefore associated with changes in detrital input. The overall decreased detrital input can be explained by the increasingly remote continental sources due to the major transgression at the end of Cenomanian, coupled with changes in continental weathering intensity linked to increasingly more arid climate conditions.

Late Barremian-Early Aptian palaeoenvironmental change: the Cassis-La Bedoule section (SE France)

The well-dated section of Cassis-La Bédoule in the South Provencal Basin (southern France) allows for a detailed reconstruction of palaeoenvironmental change during the latest Barremian and Early Aptian. For this study, phosphorus (P) and clay-mineral contents, stable-isotope ratios on carbonate (δ13Ccarb) and organic matter (δ13Corg), and redox-sensitive trace elements (RSTE: V, U, As, Co, and Mo) have been measured in this historical stratotype. The base of the section consists of rudist limestone, which is attributed to the Urgonian platform. The presence of low P and RSTE content, and content of up to 30% kaolinite indicate deposition under oligotrophic and oxic conditions, and the presence of warm, humid climatic conditions on the adjacent continent. The top of the Urgonian succession is marked by a hardground with encrusted brachiopods and bivalves, which is interpreted as a drowning surface. The section continues with a succession of limestone and marl containing the first occurrence of planktonic foraminifera. This interval includes several laminated, organic-rich layers recording RSTE enrichments and high Corg:Ptot ratios. The deposition of these organic-rich layers was associated with oxygen-depleted conditions and a large positive excursion in δ13Corg. During this interval, a negative peak in the δ13Ccarb record is observed, which dates as latest Barremian. This excursion is coeval with negative excursions elsewhere in Tethyan platform and basin settings and is explained by the increased input of light dissolved inorganic carbon by rivers and/or volcanic activity. In this interval, an increase in P content, owing to reworking of nearshore sediments during the transgression, is coupled with a decrease in kaolinite content, which tends to be deposited in more proximal areas. The overlying hemipelagic sediments of the Early Aptian Deshayesites oglanlensis and D. weissi zones indicate rather stable palaeoenvironmental conditions with low P content and stable δ13C records. A change towards marl-dominated beds occurs close to the end of the D. weissi zone. These beds display a long decrease in their δ13Ccarb and δ13Corg records, which lasted until the end of the Deshayesites deshayesi subzone (corresponding to C3 in Menegatti et al., 1998). This is followed by a positive shift during the Roloboceras hambrovi and Deshayesites grandis subzones, which corresponds in time to oceanic anoxic event (OAE) 1a interval. This positive shift is coeval with two increases in the P content. The marly interval equivalent to OAE 1a lacks organic-rich deposits and RSTE enrichments indicating that oxic conditions prevailed in this particular part of the Tethys ocean. The clay mineralogy is dominated by smectite, which is interpreted to reflect trapping of kaolinite on the surrounding platforms rather than indicating a drier climate.

Complexation of copper by sewage sludge-derived dissolved organic matter: Effects on soil sorption behaviour and plant uptake

The complexation of Cu by sewage sludge-derived dissolved organic matter (SSDOM) is a process by which the environmental significance of the element may become enhanced due to reduced soil sorption and, hence, increased mobility. The work described in this paper used an ion selective electrode procedure to show that SSDOM complexation of Cu was greatest at intermediate pH values because competition between hydrogen ions and Cu for SSDOM binding sites, and between hydroxyl ions and SSDOM as Cu ligands, was lowest at such values. Batch sorption experiments further showed that the process of Cu complexation by SSDOM provided an explanation for enhanced desorption of Cu from the solid phase of a contaminated, organic matter-rich, clay loam soil, and reduced adsorption of Cu onto the solid phase of a sandy loam soil. Complexation of Cu by SSDOM did not affect uptake of Cu by spring barley plants, when compared to free ionic Cu, in a sand-culture pot experiment. However, it did appear to lead to greater biomass yields of the plant; perhaps indicating that the Cu-SSDOM complex had a lower toxicity towards the plant than the free Cu ion.

The turnover of organic carbon in subsoils. Part 2. Modelling carbon turnover

A new model, RothPC-1, is described for the turnover of organic C in the top metre of soil. RothPC-1 is a version of RothC-26.3, an earlier model for the turnover of C in topsoils. In RothPC-1 two extra parameters are used to model turnover in the top metre of soil: one, p, which moves organic C down the profile by an advective process, and the other, s, which slows decomposition with depth. RothPC-1 is parameterized and tested using measurements (described in Part 1, this issue) of total organic C and radiocarbon on soil profiles from the Rothamsted long-term field experiments, collected over a period of more than 100 years. RothPC-1 gives fits to measurements of organic C and radiocarbon in the 0-23, 23-46, 46-69 and 69-92 cm layers of soil that are almost all within (or close to) measurement error in two areas of regenerating woodland (Geescroft and Broadbalk Wildernesses) and an area of cultivated land from the Broadbalk Continuous Wheat Experiment. The fits to old grassland (the Park Grass Experiment) are less close. Two other sites that provide the requisite pre- and post-bomb data are also fitted; a prairie Chernozem from Russia and an annual grassland from California. Roth-PC-1 gives a close fit to measurements of organic C and radiocarbon down the Chernozem profile, provided that allowance is made for soil age; with the annual grassland the fit is acceptable in the upper part of the profile, but not in the clay-rich Bt horizon below. Calculations suggest that treating the top metre of soil as a homogeneous unit will greatly overestimate the effects of global warming in accelerating the decomposition of soil C and hence on the enhanced release of CO2 from soil organic matter; more realistic estimates will be obtained from multi-layer models such as RothPC-1.

Chemical composition and in vitro fermentation of tannin-rich tree fruits

Dry and mature tree fruits are a potential source of protein for goats in the semi-arid areas of southern Africa, but their chemical composition and feeding value is largely unknown. This study presents the chemical composition and in vitro fermentation of indehiscent whole fruits and separated seed and hull fractions from Acacia nilotica, Acacia erubescens, Acacia sieberiana, Acacia erioloba, Piliostigma thonningii and Dichrostachys cinerea trees. Results indicate that the N contents of whole fruits ranged between 13.5 g/kg DM (A. nilotica) and 27.1 g/kg DM (A. erubescens). Seeds had a higher N content than hulls for all tree species. A. nilotica, D. cinerea and P thonningii fruits had high levels of extractable phenolics (758, 458 and 299 g/kg DM, respectively). Soluble phenolics (SPh) and ytterbium precipitable phenolics (YbPh) levels were negatively correlated to in vitro gas production but positively correlated to in vitro organic matter degradability (iOMD). Partition factors for whole fruits at 48 h ranged between 3.6 mg/ml for A. erioloba and 7.8 mg/ml for A. nilotica. Seeds of A. erioloba, A. erubescens and P thonningii were consistently fermented more efficiently throughout the incubation period compared to their whole fruits or hulls. Estimating in vitro degradability of phenolic-rich substrates through filtration procedures can give erroneous results due to the loss of soluble phenolics, which are not necessarily degradable. The feeding value of fruits from D. cinerea and A. nilotica tree species may be reduced due to the presence of high levels of phenolics. (C) 2007 Elsevier B.V. All rights reserved.

Organic certification, export market access and the impacts of policy: Bayesian estimation of avocado smallholder “times-to-organic certification” in Michoacán Mexico

This study analyzes organic adoption decisions using a rich set of time-to-organic durations collected from avocado small-holders in Michoacán Mexico. We derive robust, intrasample predictions about the profiles of entry and exit within the conventional-versus-organic complex and we explore the sensitivity of these predictions to choice of functional form. The dynamic nature of the sample allows us to make retrospective predictions and we establish, precisely, the profile of organic entry had the respondents been availed optimal amounts of adoption-restraining resources. A fundamental problem in the dynamic adoption literature, hitherto unrecognized, is discussed and consequent extensions are suggested.

Fat and fatty acid composition of cooked meat from UK retail chickens labelled as from organic and non-organic production systems

This study compared fat and fatty acids in cooked retail chicken meat from conventional and organic systems. Fat contents were 1.7, 5.2, 7.1 and 12.9 g/100 g cooked weight in skinless breast, breast with skin, skinless leg and leg with skin respectively, with organic meat containing less fat overall (P < 0.01). Meat was rich in cis-monounsaturated fatty acids, although organic meat contained less than did conventional meat (1850 vs. 2538 mg/100 g; P < 0.001). Organic meat was also lower (P < 0.001) in 18:3 n−3 (115 vs. 180 mg/100 g) and, whilst it contained more (P < 0.001) docosahexaenoic acid (30.9 vs. 13.7 mg/100 g), this was due to the large effect of one supermarket. This system by supermarket interaction suggests that poultry meat labelled as organic is not a guarantee of higher long chain n−3 fatty acids. Overall there were few major differences in fatty acid contents/profiles between organic and conventional meat that were consistent across all supermarkets.